Near-Infrared (NIR) transparent neutral black perylene solid solutions

- SUN CHEMICAL B.V.

The present invention relates to a solid solution comprising (a) at least one compound according to formula (I) and (b) at least one compound according to formula (II), or at least one compound according to formula (III), or a mixture of at least one compound according to formula (II) and at least one compound according to formula (III) wherein R1 and R2 may, independently of one another, stand for —(CH2)n—X, wherein X stands for hydrogen, methyl, a C1-C5 alkoxyl, hydroxy, phenyl, C1-C5 alkylphenyl, C1-C5 alkoxyphenyl, hydroxyphenyl, halogenated phenyl, pyridyl, C1-C5 alkylpyridyl, C1-C5 alkoxypyridyl, halogenated pyridyl, pyridylvinyl or naphthyl; wherein n stands for 0, 1, 2, 3, 4 or 5; R3 and R4 may, independently of one another, stand for phenylene, C1-C5 alkylphenylene, C1-C5 alkoxyphenylene, hydroxyphenylene, halogenated phenylene, pyridinediyl, C1-C5 alkylpyridinediyl, C1-C5 alkoxy-pyridinediyl, halogenated pyridinediyl, anthraquinonediyl or naphthalenediyl, wherein the 2 nitrogen atoms bound to R4 according to formula (II) and (III) form a 5-membered or a 6-membered heterocycle with 2 atoms of an aromatic ring of R3; wherein the 2 nitrogen atoms bound to R4 according to formula (II) and (III) form a 5-membered or a 6-membered heterocycle with 2 atoms of an aromatic ring of R4; X1 to X8 may, independently from one another, stand for hydrogen, C1-C5 alkyl, C1-C5 alkoxy, hydroxy, phenyl or halide. The present invention further relates to a process for producing the solid solution. Furthermore, the present invention relates to a solid solution obtainable or obtained according to said process and to the use of the inventive solid solution, in particular as a NIR transparent black colorant in a NIR non-absorbing component.

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Description
TECHNICAL FIELD

The present invention relates to a solid solution comprising at least one compound according to formula (I)

and at least one compound according to formula (II), or at least one compound according to formula (III), or a mixture of at least one compound according to formula (II) and at least one compound according to formula (III)

The present invention further relates to a process for producing the solid solution. The present invention furthermore relates to a solid solution obtainable or obtained according to said process and to the use of the inventive solid solution, in particular as a near-infrared (NIR) transparent black colorant in a near-infrared (NIR) non-absorbing component.

INTRODUCTION

For many coating applications such as automotive coatings, aerospace coatings, industrial coatings and architectural coatings, dark colors, such as black are particularly desirable for aesthetic purposes. As black pigments, there have been conventionally used carbon black such as PBk 6, PBk7 or inorganic black pigments like PBk 11. However, dark colored coatings have historically been susceptible to absorption of near-infrared radiation because they often rely on the use of pigments, such as carbon black, that absorb near-infrared radiation in addition to visible radiation. Near-infrared (NIR) radiation, i.e., electromagnetic radiation having a wavelength of from 700 to 2500 nanometers, constitutes over 50% of the solar energy that reaches the earth's surface. Heat is a direct consequence of the absorption of near-infrared (NIR) radiation. As a result, dark colored coatings have historically been susceptible to substantially increased temperatures, particularly on sunny days, which is often undesirable for many reasons.

Additionally, recent advances have been made in technologies utilizing NIR, related to self-driving (“autonomous”) vehicles and other objects in a vehicle's surroundings including markings that are detectable by a sensor mounted on the autonomous vehicle.

Traditional carbon black pigments strongly absorb near-infrared (NIR) LiDAR signals used by autonomous vehicles for navigation. Low LiDAR signal return erodes object detection capability particularly for darker colored objects that contain higher levels of carbon black. Automotive coating formulations using NIR transparent or reflective functional black pigments deliver superior signal response thereby improving object detection. However, black pigments are vital formulation tools but traditional carbon black pigments largely absorb LiDAR's signal. Dark and black shades with good LiDAR response are desired.

In addition, in WO2018/081613 attempts have been made to obtain methods and systems for increased NIR detection distance of an object coated with a NIR reflective coating using a physical mixture of different perylene-based pigments. However, even though such pigment blend of two (or more) pigments achieve the required coloristics, the coloristic obtained from the dispersed mixed pigments can vary significantly depending on the dispersion conditions used and the required tint level in the target color. In order to achieve the required coloristic at all concentrations when using a physical mixture of two (or more) pigments, generally the ratios of the blended components will need to be adjusted to achieve the same neutral coloristic. U.S. Pat. No. 7,083,675 describes perylene-based pigments as solid solutions produced by calcination at high temperatures and in vacuum or in an inert gas atmosphere. However, these pigments have low-crystallinity and insufficient coloristic performance. Additionally, due to the process conditions at high temperatures under inert gas atmosphere these pigments cannot be used conventionally in the field of organic pigments.

A solid solution defines a crystal where two or more molecules are contained within the same crystal structure and this structure is identical to that adopted by one of the molecules alone. The molecule in the greatest concentration, whose crystal structure dictates that of the solid solution, is termed as the host. The other molecule is termed as the guest. In any event, a solid solution can be differentiated from a physical mixture of the components by examination of their X-ray diffraction patterns. In a physical mixture, the X-ray diffraction patterns characteristic of each of the components are identifiable, and the pattern of the mixture is the sum of the patterns of each of the components. The X-ray diffraction pattern of a solid solution, however, is clearly distinguishable from those of its components; some of the X-ray lines of the components may disappear and new ones appear.

There, however, is a need for improved coloristics and functionality in a near-infrared (NIR) transparent black perylene-based pigment. In particular, there remains the problem of providing a near-infrared (NIR) transparent black perylene-based pigment in which the coloristic obtained from the dispersed mixed pigments does not significantly depend on the dispersion conditions used and the required pigment levels in the target color. There is a need to achieve the required coloristic at all concentrations without varying the ratios of the blended components.

DETAILED DESCRIPTION

It was therefore an object of the present invention to provide an improved solid solution, which provides colorations having advantageous performance properties, especially neutral coloristics, very low chroma and high black values (Mc color depending and My non-color depending). Thus, it has surprisingly been found that a solid solution containing near-infrared (NIR) transparent black perylene-based pigment provides colorations having advantageous performance properties, especially neutral coloristics, very low chroma and high black values (Mc color depending and My non-color depending).

Therefore, the present invention relates to a solid solution comprising (a) at least one compound according to formula (I)

and (b) at least one compound according to formula (II), or at least one compound according to formula (III), or a mixture of at least one compound according to formula (II) and at least one compound according to formula (III)

wherein R1 and R2 may, independently of one another, stand for —(CH2)n—X, wherein X stands for hydrogen, methyl, a C1-C5 alkoxyl, hydroxy, phenyl, C1-C5 alkylphenyl, C1-C5 alkoxyphenyl, hydroxyphenyl, halogenated phenyl, pyridyl, C1-C5 alkylpyridyl, C1-C5 alkoxypyridyl, halogenated pyridyl, pyridylvinyl or naphthyl; wherein n stands for 0, 1, 2, 3, 4 or 5; R3 and R4 may, independently of one another, stand for phenylene, C1-C5 alkylphenylene, C1-C5 alkoxyphenylene, hydroxyphenylene, halogenated phenylene, pyridinediyl, C1-C5 alkylpyridinediyl, C1-C5 alkoxypyridinediyl, halogenated pyridinediyl, anthraquinonediyl or naphthalenediyl, wherein the 2 nitrogen atoms bound to R3 according to formula (II) and (III) form a 5-membered or a 6-membered heterocycle with 2 atoms of an aromatic ring of R3; wherein the 2 nitrogen atoms bound to R4 according to formula (II) and (III) form a 5-membered or a 6-membered heterocycle with 2 atoms of an aromatic ring of R4; X1 to X8 may, independently from one another, stand for hydrogen, C1-C5 alkyl, C1-C5 alkoxy, hydroxy, phenyl or halide.

According to the present invention it is preferred that the 2 nitrogen atoms bound to R3 according to formula (II) and (III) form a 5-membered heterocycle with 2 adjacent atoms of an aromatic ring of R3; and the 2 nitrogen atoms bound to R4 according to formula (II) and (III) form a 5-membered heterocycle with 2 adjacent atoms of an aromatic ring of R4.

According to the present invention, it is preferred that X stands for C1-C5 alkoxyphenyl or phenyl and n is 1 or 2; R3 and R4 are independently of one another phenylene, C1-C5 alkylphenylene, C1-C5 alkoxyphenylene, halogenated phenylene or naphthalenediyl; X1 to X8 stand for independently of one another hydrogen or halide.

According to the present invention, it is preferred that X stands for methoxyphenyl or phenyl and n is 1 or 2; R3 and R4 are independently of one another phenylene, methyl-phenylene, methoxyphenylene, chloro-phenylene, dichloro-phenylene or naphthalenediyl; X1 to X8 stand for hydrogen.

According to particular and preferred embodiments of the present invention, wherein R1 and R2 may, independently from one another, stand for —CH2C6H4OCH3 or —CH2CH2C6H5; R3 and R4 may, independently of one another, stand for phenylene, 4-chloro-phenylene, naphthalenediyl or 4,5-dichloro-phenylene; X1 to X8 stand for hydrogen.

According to the present invention, it is preferred that R1 is R2 or that R3 is R4 or that R1 is R2 and R3 is R4, preferably that R1 is R2 and R3 is R4.

According to the present invention, it is preferred that X stands for 4-methoxyphenyl and n is 1; R3 and R4 stand for phenylene; X1 to X8 stand for hydrogen.

According to the present invention, it is preferred that X stands for 4-methoxyphenyl and n is 1; R3 and R4 are naphthalenediyl; X1 to X8 are hydrogen.

According to the present invention, it is preferred that X stands for 4-methoxyphenyl and n is 1; R3 and R4 stand for 4-chloro-phenylene; X1 to X8 stand for hydrogen.

According to the present invention, it is preferred that X stands for 4-methoxyphenyl and n is 1; R3 and R4 stand for 4,5-dichloro-phenylene; X1 to X8 stand for hydrogen.

According to the present invention, it is preferred that X stands for phenyl and n is 2; R3 and R4 stand for phenylene; X1 to X8 stand for hydrogen.

According to the present invention, it is preferred that X stands for phenyl and n is 2; R3 and R4 stand for naphthalenediyl; X1 to X8 stand for hydrogen.

According to the present invention, it is preferred that X stands for phenyl and n is 2; R3 and R4 stand for 4-chloro-phenylene; X1 to X8 stand for hydrogen.

According to the present invention, it is preferred that that the solid solution of the present invention exhibits a black value My in the range of from 200 to 350, preferably in the range of from 220 to 330, more preferably in the range of from 230 to 300 and a color depending black value Mc in the range of from 200 to 350, preferably in the range of from 220 to 330, more preferably in the range of from 230 to 300 My and Mc being determined according to DIN EN 18314-3.

According to the present invention, it is preferred that that the solid solution of the present invention is a black near-infrared (NIR) neutral transparent pigment of neutral hue, wherein near-infrared (NIR) represents a wavelength in the range of from 700 to 2500 nanometers, and wherein transparent represents a transparency in the near-infrared region having a transmission of >70%, preferably of 80% at 1000 nm.

According to the present invention, it is preferred that the solid solution of the present invention exhibits a TSR value over a reflective substrate (TSR value>80%) of a value of >25%, preferably of a value of >33%.

According to the present invention, it is preferred that the solid solution of the present invention exhibits a near-infrared reflectance over a reflective substrate (>90% reflectance) at 905 nm of a value of >65%, preferably of a value of >75%, over a reflective substrate (>70% reflectance) at 1550 nm of a value of >50%, preferably of a value of >60%.

According to the present invention, it is preferred that the solid solution of the present invention has a particle size in the range of from 5 to 1000 nm, preferably in the range of from 10 to 500 nm, more preferably in the range of from 20 to 200 nm.

According to the present invention, it is preferred that the solid solution of the present invention comprises, preferably consists of, one crystal modification, more preferably comprises, more preferably consists of, one crystal modification in an amount of more than 80 weight-%, more preferably in an amount of more than 90 weight-%, based on the total weight of the solid solution.

According to the present invention, it is preferred that in the solid solution, the weight ratio of the at least compound of formula (I) relative to the at least one compound according to formula (II) or to the at least one compound according to formula (III) or to the mixture of at least one compound according to formula (II) and at least one compound according to formula (III), weight((I)):weight((II)(III)), is in the range of from 60:40 to 95:5, preferably in the range of from 65:35 to 95:5, more preferably in the range of from 70:30 to 90:10, such as in the range of from 70:30 to 80:20 or in the range of from 75:25 to 85:15 or in the range o from 80:20 to 90:10.

According to the present invention, it is preferred that from 80 to 100 weight-%, preferably from 85 to 100 weight-%, more preferably from 90 to 100 weight-%, more preferably from 95 to 100 weight-%, more preferably from 98 to 100 weight-% of the solid solution consist of (a) the at least one compound according to formula (I) and (b) the at least one compound according to formula (II), or the at least one compound according to formula (III), or the mixture of the at least one compound according to formula (II) and the at least one compound according to formula (III).

According to the present invention, it is preferred that the solid solution comprises (a) one compound according to formula (I) and (b) one compound according to formula (II), or one compound according to formula (III), or a mixture of one compound according to formula (II) and one compound according to formula (III).

Alternatively, it is preferred according to the present invention that from 80 to 100 weight-%, preferably from 85 to 100 weight-%, more preferably from 90 to 100 weight-%, more preferably from 95 to 100 weight-%, more preferably from 98 to 100 weight-% of the solid solution consist of (a) one compound according to formula (I) and (b) one compound according to formula (II), or one compound according to formula (III), or a mixture of one compound according to formula (II) and one compound according to formula (III).

The present invention further relates to a process for producing a solid solution, comprising

    • (i.1) providing a compound according to formula (IV)

    • or a derivative thereof selected from the group consisting of perylene-3,4:9,10-tetracarboxylic acid, perylene-3,4:9,10-tetracarbonyl chloride, perylene-3,4:9,10-tetramethanoate, perylene-3,4:9,10-tetraethanoate, perylene-3,4:9,10-tetrapropanoate or perylene-3,4:9,10-tetrabutanoate, and a suitable organic base;
    • (i.2) simultaneously reacting the compound of formula (IV)
      • (i.2.1) with a compound R1—NH2, or with a compound R2—NH2, or, if R1 is different from R2, with a compound R1—NH2 and with a compound R2—NH2;
      • and
      • (i.2.2) with a compound H2N—R3—NH2, or with a compound H2N—R4—NH2, or, if R3 is different from R4, with a compound H2N—R3—NH2 and with a compound H2N—R4—NH2, wherein the 2 nitrogen atoms bound to R3 are bound to 2 atoms of an aromatic ring of R3 and wherein the 2 nitrogen atoms bound to R4 are bound to 2 atoms of an aromatic ring of R4;
    • wherein
    • R1 and R2 are independently of one another —(CH2)n—X, wherein X is hydrogen, methyl, a C1-C5 alkoxyl, hydroxy, phenyl, C1-C5 alkylphenyl, C1-C5 alkoxyphenyl, hydroxyphenyl, halogenated phenyl, pyridyl, C1-C5 alkylpyridyl, C1-C5 alkoxypyridyl, halogenated pyridyl, pyridylvinyl or naphthyl; wherein n is 0, 1, 2, 3, 4 or 5;
    • R3 and R4 are independently of one another phenylene, C1-C5 alkylphenylene, C1-C5 alkoxyphenylene, hydroxyphenylene, halogenated phenylene, pyridinediyl, C1-C5 alkylpyridinediyl, C1-C5 alkoxypyridinediyl, halogenated pyridinediyl, anthraquinonediyl or naphthalenediyl;
    • X1 to X8 are independently from one another hydrogen, C1-C5 alkyl, C1-C5 alkoxy, hydroxy, phenyl or halide.

According to the present invention, it is preferred that in (i.1), the compound of formula (IV) is provided as a solid, preferably as a solid admixed with a solvent, more preferably as a solid admixed with a solvent selected from the group consisting of water, diethyleneglycol, triethylenglygol, tetraethyleneglycol, butylglycol, dimethylformamide, pyridine, nitrobenzene, Therminol VP-1, 1,3-dimethyl-imidazolidin-2-one, phenol, trichlorobenzene, dichlorobenzene, mesytilene, xylene, propylbenzene, alkylnaphatalene, dimethylsulfoxide, N-methylpyrrolidone, quinoline, Nmethylimidazole or imidazole, more preferably as a solid admixed with water.

According to the present invention, it is preferred that the process further comprises, after (i.1) and before (i.2), preparing a suspension comprising the compound according to formula (IV); and the compound R1—NH2, or the compound R2—NH2, or, if R1 is different from R2, the compound R1—NH2 and the compound R2—NH2; and the compound H2N—R3—NH2, or the compound H2N—R4—NH2, or, if R3 is different from R4, the compound H2N—R3—NH2 and the compound H2N—R4—NH2; and water.

According to the present invention, it is preferred that the process further comprises, after (i.1) and before (i.2), preparing a solution comprising the compound according to formula (IV); and the compound R1—NH2, or the compound R2—NH2, or, if R1 is different from R2, the compound R1—NH2 and the compound R2—NH2; and the compound H2N—R3—NH2, or the compound H2N—R4—NH2, or, if R3 is different from R4, the compound H2N—R3—NH2 and the compound H2N—R4—NH2, and a suitable inorganic base, preferably potassium hydroxide, and sodium hydrosulfite.

According to the present invention, it is preferred that the suitable organic base comprises a secondary or tertiary amine, preferably is selected from the group consisting of piperazine, N-(2-hydroxyethyl)piperazine, diethanolamine, N,N′-dimethylpiperazine, N-ethylpiperazine, N-methylcyclohexylamine, imidazole, N-methylimidazole and pyrrolidine, more preferably is piperazine.

Further, it is preferred according to the present invention that the reaction according to (i.2) is carried out in the presence of 95 to 5 weight-%, preferably 90 to 10 weight-%, more preferably 80 to 20 weight-%, more preferably 70 to 30 weight-% of the compound R1—NH2, or of the compound R2—NH2, or, if R1 is different from R2, of the compound R1—NH2 and of the compound R2—NH2; and in the presence of 5 to 95 weight-%, preferably 10 to 90 weight-%, more preferably 20 to 80 weight-%, more preferably 30 to 70 weight-% of the compound H2N—R3—NH2, or the compound H2N—R4—NH2, or, if R3 is different from R4, the compound H2N—R3—NH2 and the compound H2N—R4—NH2.

According to the present invention, it is preferred that the reaction according to (i.2) is carried out at a temperature of the reaction mixture, preferably of the suspension as defined in embodiment 24 or 25, in the range of from 60 to 210° C., preferably in the range of from 150 to 200° C., at a pressure in the range of from 1 to 20 bar (100 to 2000 kPa), preferably in the range of from 1 to 16 bar (100 to 16000 kPa).

According to the present invention, it is preferred that the reaction according to (i.2) is carried out in a mixing apparatus, preferably in single or multishaft kneaders, more preferably in a kneaderlike reactor, a single- or multi-part/shaft kneader, an extruder, a paddle dryer, a mixer or a mill.

Alternatively, according to the present invention, it is preferred that the reaction according to (i.2) is carried out in melt-mixing assemblies, preferably in screw kneaders, such as single-screw kneaders (for example co-kneaders, single-screw extruders, in particular with mixing and shearing sections), twin-screw kneaders (for example ZSK or ZE twin-screw extruders, kombiplast extruders, MPC twin-screw kneader mixers, FCM two-stage mixers, KEX kneading screw extruders, and heavy roll extruders). Kneaders with or without a ram are also suitable, as are trough kneaders and Banbury mixers.

According to the present invention, it is preferred that during the reaction according to (i.2) said temperature and said pressure are at least two of the following combinations of ranges: a temperature in the range of from 150 to 220° C. and a pressure in the range of from 9 to 13 bar (900 to 1300 kPa); a temperature in the range of from 170 to 190° C. and a pressure in the range of from 10 to 12 bar (1000 to 1200 kPa); a temperature in the range of from 80 to 120° C. and a pressure in the range of from 1 to 1.5 bar (100 to 150 kPa).

According to the present invention, it is preferred that the process further comprises (i.3) cooling the reaction mixture obtained from (i.2), preferably to a temperature of the mixture in the range of from 15 to 40° C., more preferably in the range of from 20 to 30° C.

According to the present invention, it is preferred that the process further comprises (i.4) admixing the reaction mixture obtained from (i.2), preferably the cooled reaction mixture obtained from (i.3), with water and a suitable salt, and heating the obtained mixture, preferably to a temperature in the range of from 50 to 90° C., more preferably in the range of from 60 to 80° C., obtaining a suspension, wherein the suitable salt is potassium carbonate.

According to the present invention, it is preferred that the process further comprises (i.5) subjecting the mixture obtained from (i.2), preferably from (i.3), more preferably from (i.4), to solid-liquid separation, said solid-liquid separation preferably comprising one or more of centrifugation and filtration, more preferably filtration; (i.6) washing the solids obtained from (i.5) with at least one suitable washing agent, said suitable washing agent preferably comprising water, more preferably comprising water and at least one suitable organic acid, wherein said at least one suitable organic acid, comprises, more preferably is, acetic acid and citric acid; (i.7) drying the solids obtained from (i.6) in a gas atmosphere, said gas atmosphere preferably being one or more of nitrogen, air, and lean air and preferably having a temperature in the range of from 50 to 95° C., more preferably 60 to 90° C., more preferably 70 to 85° C.

According to the present invention, it is preferred that the process further comprises (i) providing a mixture comprising the solid solution obtainable or obtained according to the process as described in any of the particular and preferred embodiments described in the present description; preferably providing a mixture comprising the solid solution obtainable or obtained from (1.2), more preferably from (i.3), more preferably from (i.4), more preferably from (i.5), more preferably from (i.6), more preferably from (i.7), (ii) subjecting the mixture provided according to (i) to mechanical treatment; (iii) adding water to the mixture obtained from (ii); (iv) subjecting the mixture obtained from (iii) to solid-liquid separation; (v) washing the solids obtained from (iv) with at least one suitable washing agent; (vi) drying the solids obtained from (v), obtaining the solid solution.

According to the present invention, it is preferred that providing a mixture according to (i) comprises adding at least one suitable acid or solvent to the mixture, wherein the at least one suitable acid is preferably one or more of polyphosphoric acid and sulfuric acid, wherein more preferably, the at least one suitable acid comprises, more preferably is sulfuric acid, and wherein the at least one solvent comprises, preferably is water.

According to the present invention, it is preferred that providing a mixture according to (i) is carried out at a temperature of the mixture in the range of from 30 to 120° C., preferably in the range of from 40 to 110° C., more preferably in the range of from 50 to 100° C.

According to the present invention, it is preferred that providing a mixture according to (i) is carried out at a temperature of the mixture in the range of from 30 to 80° C., preferably in the range of from 40 to 70° C., more preferably in the range of from 45 to 60° C., the process preferably further comprises adding at least one suitable base, solvent or sodium hydrosulfite to the mixture, wherein the at least one suitable base is preferably one or more of sodium hydroxide and potassium hydroxide, wherein more preferably, the at least one suitable base is sodium hydroxide, and wherein the at least one solvent comprises, preferably is water, more preferably wherein the process further comprises adding at least one suitable oxidant, wherein more preferably, the at least one suitable oxidant is one or more of oxygen or hydrogen peroxide.

According to the present invention, it is preferred that the mechanical treatment according to (ii) comprises one or more kneading and milling, wherein kneading comprises coextrusion, salt kneading, single-shaft kneading and double-shaft kneading and wherein milling comprises wet milling, ball milling, bead milling, vibration milling, planetary milling and attritor milling.

According to the present invention, it is preferred that the mechanical treatment according to (ii) comprises, preferably is kneading, wherein said kneading is carried out at a temperature of the mixture in the range of from 40 to 120° C., preferably in the range of from 45 to 90° C., more preferably in the range of from 50 to 90° C., the process preferably further comprising, either directly before and/or during kneading, adding one or suitable solvent or adding one or more of sodium chloride, sodium sulfate and anhydrous aluminium sulfate, preferably sodium chloride to the mixture to be kneaded, wherein more preferably the weight ratio of one or more of sodium chloride, sodium sulfate and anhydrous aluminium sulfate relative to the mixture provided according to (i), is in the range of from 20:1 to 1:1, preferably 15:1 to 2:1, more preferably 10:1 to 2:1, more preferably 8:1 to 2:1, more preferably 6:1 to 2:1, and more preferably 4:1 to 2:1, and wherein the at least one solvent is preferably one or more ethylene glycol, diethylene glycol, diacetone alcohol, dimethylformamide, glycerine, triethylene glycol, dipropylene glycol, ethylene glycol monobutyl ether, methyl ethyl ketone, cyclohexanone, dimethylacetamide, N-methylpyrrolidone, butyl acetate, glycerol triacetate, sulfolane, xylene, tetrahydrofuran, butanol, water and dimethyl sulfoxide, wherein more preferably, the at least one solvent comprises, more preferably is diethylene glycol, diacetone alcohol, dimethylformamide, xylene, butanol, water and glycerine.

According to the present invention, it is preferred that the mechanical treatment according to (ii) further comprises, either directly before and/or during kneading, adding at least one or more of a synergist comprising sulfonic and carboxylic acid derivatives of perylene, indanthrone, phthalocyanine and diketopyrrolopyrrole, preferably in an amount of 1 to 15 weight-%, more preferably 1 to 5 weight-%, based on the total weight of the kneaded mixture, and/or a natural or synthetic resin comprising esters and salts of abietic acid, hydrated or hydrogenated or partially hydrogenated or dimerised rosin, preferably in an amount of 1 to 50 weight-%, more preferably 2 to 25 weight-%, based on the total weight of the kneaded mixture; or polysorbate nonionic surfactant comprising an ester or a mixture of esters comprising lauric or sebacic acid comprising sorbitan monolaureate or dibutylsebacate polyols, preferably in an amount of 1 to 50 weight-%, more preferably 2 to 20 weight-%, based on the total weight of the kneaded mixture, to the mixture to be kneaded.

Alternatively, it is preferred according to the present invention that the mechanical treatment according to (ii) comprises, preferably is milling, wherein said milling is carried out at a temperature of the mixture in the range of from 40 to 120° C., preferably in the range of from 45 to 90° C., more preferably in the range of from 50 to 90° C., the process preferably further comprising, either directly before and/or during milling, adding one or more of sodium chloride, sodium sulfate and anhydrous aluminium sulfate, preferably sodium chloride to the mixture to be milled.

According to the present invention, it is preferred that the process further comprises, directly after milling, adding at least one suitable acid or solvent to the milled mixture under stirring at a temperature of the mixture in the range of from 40 to 200° C., preferably in the range of from 45 to 150° C., more preferably in the range of from 50 to 120° C., wherein the at least one suitable acid is preferably one or more of polyphosphoric acid and sulfuric acid, wherein more preferably, the at least one suitable acid comprises, more preferably is sulfuric acid, and wherein the at least one solvent is preferably one or more ethylene glycol, diethylene glycol, diacetone alcohol, dimethylformamide, glycerine, triethylene glycol, dipropylene glycol, ethylene glycol monobutyl ether, methyl ethyl ketone, cyclohexanone, dimethylacetamide, N-methylpyrrolidone, butyl acetate, glycerol triacetate, sulfolane, xylene, tetrahydrofuran, butanol, water and dimethyl sulfoxide, wherein more preferably, the at least one solvent comprises, more preferably is diethylene glycol, diacetone alcohol, dimethylformamide, xylene, tetrahydrofuran, butanol, water and glycerine.

According to the present invention, it is preferred that milling is carried out with steel balls, silicon/aluminum/zirconium oxide beads, glass beads, ceramic beads and agate balls, preferably having a diameter in the range from 0.1 to 5 cm, and wherein milling is wet milling and wherein wet milling is carried out in water or in a mixture of water and at least one suitable organic solvent, and optionally at least one suitable base, wherein more preferably, the at least one suitable solvent comprises, more preferably is methanol, ethanol, propanol, isopropanol butanol, pentanol, ethylene glycol, diethylene glycol, triethylene glycol and dipropylene glycol, and wherein more preferably, the at least one suitable base comprises, more preferably is, sodium hydroxide, potassium hydroxide, sodium hydroxide, lithium hydroxide and benzyl trimethylammonium hydroxide.

Further, it is preferred according to the present invention that the mechanical treatment according to (ii) further comprises, either directly before and/or during milling, adding one or more of a synergist, preferably in an amount of 1 to 15 weight-%, more preferably 1 to 5 weight-%, based on the total weight of the milled mixture, and/or a natural or synthetic resin comprising esters and salts of abietic acid, hydrated or partially hydrogenated or dimerised rosin, preferably in an amount of 1 to 50 weight-%, more preferably 5 to 30 weight-% based on the total weight of the milled mixture, and a natural rosin comprising derivative of abietic acid, preferably in an amount of 1 to 50 weight-%, more preferably 5 to 30 weight-%, based on the total weight of the milled mixture, to the mixture to be milled.

According to the present invention, it is preferred that at least one or more of a synergist comprises sulfonic and carboxylic acid derivatives of perylene, indanthrone (PB 60), copper, aluminium or zinc phthalocyanine, quinacridone (PV 19, PR 202), dioxazine (PV 23, PV 37, PB 80) and diketopyrrolopyrrole (PR 254, PR 255).

Further, it is preferred according to the present invention that the at least one or more of a synergist comprises sulfonic and carboxylic acid derivatives of perylene, indanthrone, copper, aluminium or zinc phthalocyanine, quinacridone, dioxazine and diketopyrrolopyrrole, wherein the sulfonic and carboxylic acid derivatives of perylene, indanthrone, copper, aluminium or zinc phthalocyanine, quinacridone, dioxazine and diketopyrrolopyrrole may, independently of one another, be mono- or polysubstituted by —COO−M+, —COOR′5, —CONR′5R′6, —COO−N+R′5R′6R′7R′8, —SO2NR′5R′6, —CH2NR′5R′6, —CH2N+R′5R′6R′7R′8R′5—COO− and/or —CH2R′9, benzoyl and may additionally stand for mono- or polysubstituted by C1-C12-alkyl, C1-C6-alkoxy, nitro and/or halogen; R′5, R′6, R′7, R′8 may, independently of one another, stand for hydrogen; C1-C12-alkyl or C2-C12-alkenyl whose hydrocarbon chain may in each case be interrupted by one or more —O—, —S—, —NR′9—, —CO— or —SO2— moieties, and/or be mono- or polysubstituted by hydroxyl, halogen, aryl, C1-C4-alkoxy and/or acetyl; C3-C8-cycloalkyl whose carbon skeleton may be interrupted by one or more —O—, —S—, —NR′10— or —CO— moieties, and/or be substituted by acetyl; R′9 stands for phthalimidyl; R′10 stands for hydrogen or C1-C8-alkyl; M+ stands for hydrogen or a metal cation, in particular as alkali metal cation, more preferably sodium or potassium. Suitable synergists are described in EP0636666B1, preferably perylene derivative of formula I, WO2005078023A2, preferably perylene derivative of formulae Ia′ and Ib′; WO91/02034A1, preferably perylene derivative of formula I; EP2316886A1, preferably compounds of formulae DS-1, DS-2, DS-3; EP504922A1, preferably compounds of formula I; US2012018687A1, preferably compounds of formula I; US20050001202A1, preferably compounds of formulae I to VII; EP0700420B1, preferably compounds of formulae I to VII or CN110591445A, preferably compounds of formulae I, IA, IB, II, III, IV.

According to the present invention, it is preferred that the solid-liquid separation according to (iv) comprises one or more of centrifugation and filtration, more preferably filtration.

According to the present invention, it is preferred that the at least one suitable washing agent according to (v) comprises, more preferably is water, wherein the solids obtained from (iv) are preferably washed until the water obtained from washing exhibits a conductivity of at most 100 microSiemens/cm.

Furthermore, it is preferred according to the present invention that, wherein drying the solids obtained from (v) is carried out in a gas atmosphere, said gas atmosphere preferably being one or more of nitrogen, air, and lean air and preferably having a temperature in the range of from 50 to 95° C., more preferably 60 to 90° C., more preferably 70 to 85° C.

According to the present invention, it is preferred that in the process n, X, R1, R2, R3, R4, X1 to X8 and specific combinations thereof are as defined for a solid solution as described in any of the particular and preferred embodiments described in the present description.

According to the present invention, it is preferred that the solid solution is the solid solution as described in any of the particular and preferred embodiments described in the present description.

The present invention further relates to a solid solution obtainable or obtained according to the process as described in any of the particular and preferred embodiments described in the present description.

According to the present invention, it is preferred that the solid solution obtainable or obtained according to the process as described in any of the particular and preferred embodiments described in the present description, wherein R1 and R2 may, independently of one another, stand for —(CH2)n—X, wherein X stands for hydrogen, methyl, a C1-C5 alkoxyl, hydroxy, phenyl, C1-C5 alkylphenyl, C1-C5 alkoxyphenyl, hydroxyphenyl, halogenated phenyl, pyridyl, C1-C5 alkylpyridyl, C1-C5 alkoxypyridyl, halogenated pyridyl, pyridylvinyl or naphthyl; wherein n is 0, 1, 2, 3, 4 or 5; R3 and R4 may, independently of one another, stand for phenylene, C1-C5 alkylphenylene, C1-C5 alkoxyphenylene, hydroxyphenylene, halogenated phenylene, pyridinediyl, C1-C5 alkylpyridinediyl, C1-C5 alkoxypyridinediyl, halogenated pyridinediyl, anthraquinonediyl or naphthalenediyl, wherein the 2 nitrogen atoms bound to R3 according to formula (II) and (III) form a 5-membered or a 6-membered heterocycle with 2 atoms of an aromatic ring of R3; wherein the 2 nitrogen atoms bound to R4 according to formula (II) and (III) form a 5-membered or a 6-membered heterocycle with 2 atoms of an aromatic ring of R4; X1 to X8 may, independently from one another, stand for hydrogen, C1-C5 alkyl, C1-C5 alkoxy, hydroxy, phenyl or halide.

The present invention further relates to a solid solution comprised in one or more of a thermoplastic, elastomeric, crosslinked or inherently crosslinked polymer, preferably a polyolefin, polyamide, polyurethane, polyacrylate, polyacrylamide, polyvinyl alcohol, polycarbonate, polystyrene, polyester, polyacetal, a natural or synthetic rubber and a halogenated vinyl polymer in an amount from 0.01 weight-% to 70 weight-% based on the total weight of the polymer.

The present invention further relates to a solid solution comprised in one or more of a coating composition which is applied to the surface of the substrate, preferably a thermoplastic, elastomeric, crosslinked or inherently crosslinked polymer which is in the form of a film or coating applied to the surface of a substrate, or in the form of a fiber, sheet or other moulded or shaped article.

The present invention furthermore relates to a solid solution comprised in one or more of a coating composition, a light detection and ranging (LiDAR) device, a near-infrared (NIR) non-absorbing component, a photovoltaic component, a heat management component, a thermal insulation component, a coloring paint, a printing ink, a recyclable plastic article, a biodegradable mulch, a toner, a charge-generating material, a color filter, a LC display and a security print component.

The present invention further relates to a solid solution for use as a component in one or more of a coating composition, a light detection and ranging (LiDAR) device, a near-infrared (NIR) non-absorbing component, a photovoltaic component, a heat management component, a thermal insulation component, a coloring paint, a printing ink, a recyclable plastic article, a biodegradable mulch, a toner, a charge-generating material, a color filter, a LC display and a security print component.

Yet, in another embodiment, the present invention relates to the use of a solid solution as a component of one or more of a coating composition, a light detection and ranging (LiDAR) device, a near-infrared (NIR) non-absorbing component, a photovoltaic component, a heat management component, a thermal insulation component, a coloring paint, a printing ink, a recyclable plastic article, a biodegradable mulch, a toner, a charge-generating material, a color filter, a LC display and a security print component.

Alternatively, the present invention relates to a coating composition and/or a light detection and/or a ranging (LiDAR) device and/or a near-infrared (NIR) non-absorbing component and/or a photovoltaic component and/or a heat management component and/or a thermal insulation component and/or a coloring paint and/or a printing ink and/or a recyclable plastic article and/or a biodegradable mulch and/or a toner and/or a charge-generating material and/or a color filter and/or a LC display and/or a security print component, comprising a solid solution as described in any of the particular and preferred embodiments described in the present description.

The present invention further relates to a multilayer coating comprising a primer coating comprising a solid solution as described in any of the particular and preferred embodiments described in the present description and a white pigment or a reflective pigment having a reflectance of >50% in the range of 700 to 2500 nm in a weight ratio of from 1:99 to 99:1, preferably from 1:95 to 95:1; a basecoat comprising a black, preferably comprising a solid solution as described in any of the particular and preferred embodiments described in the present description, colour, metallic or interference pigment; and optionally a clear topcoat.

The present invention further relates to the use of a solid solution as described in any of the particular and preferred embodiments described in the present description for producing one or more of a coating composition, a light detection and ranging (LiDAR) device, a near-infrared (NIR) non-absorbing component, a near-infrared (NIR) non-absorbing component, a photovoltaic component, a heat management component, a thermal insulation component, coloring paint, a printing ink, a plastic, a recyclable plastic article, a biodegradable mulch, a toner, a charge-generating material, a color filter, a LC display and a security print component.

The present invention furthermore relates to a to a method for producing one or more of a coating composition, a light detection and ranging (LiDAR) device, a near-infrared (NIR) non-absorbing component, a photovoltaic component, a heat management component, a thermal insulation component, a coloring paint, a printing ink, a plastic, a recyclable plastic article, a biodegradable mulch, a toner, charge-generating material, a color filter, a LC display and a security print component, the method comprising providing and processing a solid solution as in any of the particular and preferred embodiments described in the present description.

The present invention further relates to a method for identifying an item, wherein said item comprises a feature comprising an effective amount of a solid solution as described in any of the particular and preferred embodiments described in the present description, wherein said feature is recorded under irradiation by electromagnetic waves of wavelength from 700 to 2500 nm, and the feature's image is used for identifying the item.

The present invention furthermore relates to a method for laser welding an article, wherein a solid solution as described in any of the particular and preferred embodiments described in the present description, is incorporated into a polymeric composition which is in contact with a surface of a meltable substrate containing a near infra-red absorbing material, then near infra-red radiation preferably from a laser of wavelength in the range from 700 to 2500 nm is passed through the layer containing the solid solution as described in any of the particular and preferred embodiments described in the present description to the underlying substrate generating enough heat at the point of irradiation to melt together the two materials.

The present invention furthermore relates to a method of identifying a recyclable plastic article comprising a solid solution as described in any of the particular and preferred embodiments described in the present description with a laser signal of a wavelength in the range from 700 to 2500 nm.

The present invention further relates to the use of a solid solution as described in any of the particular and preferred embodiments described in the present description as a near-infrared (NIR) transparent colorant which can replace near-infrared (NIR) absorbing black pigments in a coating or object to increase the signal to noise ratio in near-infrared (NIR) radiation detection.

The present invention further relates to the use of a solid solution as described in any of the particular and preferred embodiments described in the present description for a LiDAR detection with a laser signal of a wavelength in the range from 700 to 2500 nm.

The present invention further relates to a coating comprising a solid solution as described in any of the particular and preferred embodiments described in the present description and at least one organic pigment and/or at least one inorganic pigment and/or an effect pigment, wherein the organic pigment is selected from the group consisting of Color Index (C.I.) Pigment Yellow 109, 110, 139, 151, 154; C.I. Pigment Orange 61, 64, 69, 73; C.I. Pigment Red 122, 179, 202, 254, 264, 272, 282; C.I. Pigment Brown 29; C.I. Pigment Violet 19, 23, 37; C.I. Pigment Blue 15:1, 15:2, 15:3, 15:4, 15:6, 60, 80; C.I. Pigment Green 7, 36; C.I. Pigment Black 31, 32, Spectrasense™ Black K 0087 (Lumogen® Black K 0087) and pigment preparations of said pigments; and wherein the inorganic pigment is selected from the group consisting of C.I. Pigment Yellow 53, 184, C.I. Pigment Brown 24, 29, 33, 35, C.I. Pigment Blue 28, 36, C.I. Pigment Green 17, 26, 50, C.I. Pigment Black 12, 30 and pigment preparations of said pigments.

The present invention is illustrated by the following set of embodiments and combinations of embodiments resulting from the dependencies and back-references as indicated. In particular, it is noted that in each instance where a range of embodiments is mentioned, for example in the context of a term such as “The solid solution of any one of embodiments 1 to 4”, every embodiment in this range is meant to be explicitly disclosed for the skilled person, i.e. the wording of this term is to be understood by the skilled person as being synonymous to “The solid solution of any one of embodiments 1, 2, 3 and 4”. Further, it is explicitly noted that the following set of embodiments is not the set of claims determining the extent of protection, but represents a suitably structured part of the description directed to general and preferred aspects of the present invention.

According to an embodiment 1, the present invention relates to a solid solution comprising

    • (a) at least one compound according to formula (I)

      • and
    • (b) at least one compound according to formula (II), or at least one compound according to formula (III), or a mixture of at least one compound according to formula (II) and at least one compound according to formula (III)

wherein R1 and R2 are independently of one another —(CH2)n—X, wherein X is hydrogen, methyl, a C1-C5 alkoxyl, hydroxy, phenyl, C1-C5 alkylphenyl, C1-C5 alkoxyphenyl, hydroxyphenyl, halogenated phenyl, pyridyl, C1-C5 alkylpyridyl, C1-C5 alkoxypyridyl, halogenated pyridyl, pyridylvinyl or naphthyl; wherein n is 0, 1, 2, 3, 4 or 5; R3 and R4 are independently of one another phenylene, C1-C5 alkylphenylene, C1-C5 alkoxyphenylene, hydroxyphenylene, halogenated phenylene, pyridinediyl, C1-C5 alkylpyridinediyl, C1-C5 alkoxypyridinediyl, halogenated pyridinediyl, anthraquinonediyl or naphthalenediyl, wherein the 2 nitrogen atoms bound to R3 according to formula (II) and (III) form a 5-membered or a 6-membered heterocycle with 2 atoms of an aromatic ring of R3; wherein the 2 nitrogen atoms bound to R4 according to formula (II) and (III) form a 5-membered or a 6-membered heterocycle with 2 atoms of an aromatic ring of R4; X1 to X8 are independently from one another hydrogen, C1-C5 alkyl, C1-C5 alkoxy, hydroxy, phenyl or halide.

A preferred embodiment 2 concretizing embodiment 1, wherein X is C1-C5 alkoxyphenyl or phenyl and n is 1 or 2; R3 and R4 are independently of one another phenylene, C1-C5 alkylphenylene, C1-C5 alkoxyphenylene, halogenated phenylene or naphthalenediyl; X1 to X8 are independently of one another hydrogen or halide.

A preferred embodiment 3 concretizing embodiment 1 or 2, wherein X is methoxyphenyl or phenyl and n is 1 or 2; R3 and R4 are independently of one another phenylene, methylphenylene, methoxy-phenylene, chloro-phenylene, dichloro-phenylene or naphthalenediyl; X1 to X8 are hydrogen.

A preferred embodiment 4 concretizing any one of embodiments 1 to 3, wherein R1 and R2 are independently from one another —CH2C6H4OCH3 or —CH2CH2C6H5; R3 and R4 are independently of one another phenylene, 4-chloro-phenylene, naphthalenediyl or 4,5-dichloro-phenylene; X1 to X8 are hydrogen.

A preferred embodiment 5 concretizing any one of embodiments 1 to 4, wherein R1 is R2 or wherein R3 is R4 or wherein R1 is R2 and R3 is R4, preferably wherein R1 is R2 and R3 is R4.

A preferred embodiment 6 concretizing any one of embodiments 1 to 5, wherein X is 4-methoxyphenyl and n is 1; R3 and R4 are phenylene; X1 to X8 are hydrogen.

A preferred embodiment 7 concretizing any one of embodiments 1 to 5, wherein X is 4-methoxyphenyl and n is 1; R3 and R4 are naphthalenediyl; X1 to X8 are hydrogen.

A preferred embodiment 8 concretizing any one of embodiments 1 to 5, wherein X is 4-methoxyphenyl and n is 1; R3 and R4 are 4-chloro-phenylene; X1 to X8 are hydrogen.

A preferred embodiment 9 concretizing any one of embodiments 1 to 5, wherein X is 4-methoxyphenyl and n is 1; R3 and R4 are 4,5-dichloro-phenylene; X1 to X8 are hydrogen.

A preferred embodiment 10 concretizing any one of embodiments 1 to 5, wherein X is phenyl and n is 2; R3 and R4 are phenylene; X1 to X8 are hydrogen.

A preferred embodiment 11 concretizing any one of embodiments 1 to 5, wherein X is phenyl and n is 2; R3 and R4 are naphthalenediyl; X1 to X8 are hydrogen.

A preferred embodiment 12 concretizing any one of embodiments 1 to 5, wherein X is phenyl and n is 2; R3 and R4 are 4-chloro-phenylene; X1 to X8 are hydrogen.

A preferred embodiment 13 concretizing any one of embodiments 1 to 12, exhibiting a black value My in the range of from 200 to 350, preferably in the range of from 220 to 330, more preferably in the range of from 230 to 300 and a color depending black value Mc in the range of from 200 to 350, preferably in the range of from 220 to 330, more preferably in the range of from 230 to 300 My and Mc being determined according to DIN EN 18314-3.

A preferred embodiment 14 concretizing any one of embodiments 1 to 13, being a black near-infrared (NIR) neutral transparent pigment, wherein near-infrared represents a wavelength in the range of from 700 to 2500 nanometers, and wherein transparent represents a transparency in the near-infrared region having a transmission of >70%, preferably of 80% at 1000 nm.

A preferred embodiment 15 concretizing any one of embodiments 1 to 14, exhibiting a TSR value over a reflective substrate (TSR value>80%) of a value of >25%, preferably of a value of >33%.

A preferred embodiment 16 concretizing any one of embodiments 1 to 15, exhibiting a near-infrared reflectance over a reflective substrate (>90% reflectance) at 905 nm of a value of >65%, preferably of a value of >75%, over a reflective substrate (>70% reflectance) at 1550 nm of a value of >50%, preferably of a value of >60%.

A preferred embodiment 17 concretizing any one of embodiments 1 to 16, wherein the particle size is in the range of from 5 to 1000 nm, preferably in the range of from 10 to 500 nm, more preferably in the range of from 20 to 200 nm.

A preferred embodiment 18 concretizing any one of embodiments 1 to 17, wherein the solid solution comprises, preferably consists of, one crystal modification, more preferably comprises, more preferably consists of, one crystal modification in an amount of more than 80 weight-%, more preferably in an amount of more than 90 weight-%, based on the total weight of the solid solution.

preferred embodiment 19 concretizing any one of embodiments 1 to 18, wherein in the solid solution, the weight ratio of the at least compound of formula (I) relative to the at least one compound according to formula (II) or to the at least one compound according to formula (III) or to the mixture of at least one compound according to formula (II) and at least one compound according to formula (III), weight((I)):weight((II)(III)), is in the range of from 60:40 to 95:5, preferably in the range of from 65:35 to 95:5, more preferably in the range of from 70:30 to 90:10, such as in the range of from 70:30 to 80:20 or in the range of from 75:25 to 85:15 or in the range o from 80:20 to 90:10.

A preferred embodiment 20 concretizing any one of embodiments 1 to 19, wherein from 80 to 100 weight-%, preferably from 85 to 100 weight-%, more preferably from 90 to 100 weight-%, more preferably from 95 to 100 weight-%, more preferably from 98 to 100 weight-% of the solid solution consist of

    • (a) the at least one compound according to formula (I) and
    • (b) the at least one compound according to formula (II), or the at least one compound according to formula (III), or the mixture of the at least one compound according to formula (II) and the at least one compound according to formula (III).

A preferred embodiment 21 concretizing any one of embodiments 1 to 20, comprising

    • (a) one compound according to formula (I) and
    • (b) one compound according to formula (II), or one compound according to formula (III), or a mixture of one compound according to formula (II) and one compound according to formula (III).

A preferred embodiment 22 concretizing any embodiments 21, wherein from 80 to 100 weight-%, preferably from 85 to 100 weight-%, more preferably from 90 to 100 weight-%, more preferably from 95 to 100 weight-%, more preferably from 98 to 100 weight-% of the solid solution consist of

    • (a) one compound according to formula (I) and
    • (b) one compound according to formula (II), or one compound according to formula (III), or a mixture of one compound according to formula (II) and one compound according to formula (III).

According to an embodiment 23, the present invention relates to a process for producing a solid solution, comprising

    • (i.1) providing a compound according to formula (IV)

    • or a derivative thereof selected from the group consisting of perylene-3,4:9,10-tetracarboxylic acid, perylene-3,4:9,10-tetracarbonyl chloride, perylene-3,4:9,10-tetramethanoate, perylene-3,4:9,10-tetraethanoate, perylene-3,4:9,10-tetrapropanoate or perylene-3,4:9,10-tetrabutanoate, and a suitable organic base;
    • (i.2) simultaneously reacting the compound of formula (IV)
      • (i.2.1) with a compound R1—NH2, or with a compound R2—NH2, or, if R1 is different from R2, with a compound R1—NH2 and with a compound R2—NH2; and
      • (i.2.2) with a compound H2N—R3—NH2, or with a compound H2N—R4—NH2, or, if R3 is different from R4, with a compound H2N—R3—NH2 and with a compound H2N—R4—NH2, wherein the 2 nitrogen atoms bound to R3 are bound to 2 atoms of an aromatic ring of R3 and wherein the 2 nitrogen atoms bound to R4 are bound to 2 atoms of an aromatic ring of R4;
        wherein R1 and R2 are independently of one another —(CH2)n—X, wherein X is hydrogen, methyl, a C1-C5 alkoxyl, hydroxy, phenyl, C1-C5 alkylphenyl, C1-C5 alkoxyphenyl, hydroxyphenyl, halogenated phenyl, pyridyl, C1-C5 alkylpyridyl, C1-C5 alkoxypyridyl, halogenated pyridyl, pyridylvinyl or naphthyl; wherein n is 0, 1, 2, 3, 4 or 5; R3 and R4 are independently of one another phenylene, C1-C5 alkylphenylene, C1-C5 alkoxyphenylene, hydroxyphenylene, halogenated phenylene, pyridinediyl, C1-C5 alkylpyridinediyl, C1-C5 alkoxypyridinediyl, halogenated pyridinediyl, anthraquinonediyl or naphthalenediyl; X1 to X8 are independently from one another hydrogen, C1-C5 alkyl, C1-C5 alkoxy, hydroxy, phenyl or halide.

A preferred embodiment 24 concretizing embodiment 23, wherein the according to (i.1), the compound of formula (IV) is provided as a solid, preferably as a solid admixed with a solvent, more preferably as a solid admixed with a solvent selected from the group consisting of water, diethyleneglycol, triethylenglygol, tetraethyleneglycol, butylglycol, dimethylformamide, pyridine, nitrobenzene, Therminol VP-1, 1,3-dimethyl-imidazolidin-2-one, phenol, trichlorobenzene, dichlorobenzene, mesytilene, xylene, propylbenzene, alkylnaphatalene, dimethylsulfoxide, N-methylpyrrolidone, quinoline, N-methylimidazole or imidazole, more preferably as a solid admixed with water.

A preferred embodiment 25 concretizing embodiment 23 or 24, further comprising, after (i.1) and before (i.2), preparing a suspension comprising the compound according to formula (IV); and the compound R1—NH2, or the compound R2—NH2, or, if R1 is different from R2, the compound R1—NH2 and the compound R2—NH2; and the compound H2N—R3—NH2, or the compound H2N—R4—NH2, or, if R3 is different from R4, the compound H2N—R3—NH2 and the compound H2N—R4—NH2; and water.

A preferred embodiment 26 concretizing any one of embodiments 23 to 25, further comprising, after (i.1) and before (i.2), preparing a solution comprising the compound according to formula (IV); and the compound R1—NH2, or the compound R2—NH2, or, if R1 is different from R2, the compound R1—NH2 and the compound R2—NH2; and the compound H2N—R3—NH2, or the compound H2N—R4—NH2, or, if R3 is different from R4, the compound H2N—R3—NH2 and the compound H2N—R4—NH2, and a suitable inorganic base, preferably potassium hydroxide, and sodium hydrosulfite.

A preferred embodiment 27 concretizing any one of embodiments 23 to 26, wherein the suitable organic base comprises a secondary or tertiary amine, preferably is selected from the group consisting of piperazine, N-(2-hydroxyethyl)piperazine, diethanolamine, N,N′-dimethylpiperazine, N-ethylpiperazine, N-methylcyclohexylamine, imidazole, N-methylimidazole and pyrrolidine, more preferably is piperazine.

A preferred embodiment 28 concretizing any one of embodiments 23 to 27, wherein the reaction according to (i.2) is carried out in the presence of 95 to 5 weight-%, preferably 90 to 10 weight-%, more preferably 80 to 20 weight-%, more preferably 70 to 30 weight-% of the compound R1—NH2, or of the compound R2—NH2, or, if R1 is different from R2, of the compound R1—NH2 and of the compound R2—NH2; and in the presence of 5 to 95 weight-%, preferably 10 to 90 weight-%, more preferably 20 to 80 weight-%, more preferably 30 to 70 weight-% of the compound H2N—R3—NH2, or the compound H2N—R4—NH2, or, if R3 is different from R4, the compound H2N—R3—NH2 and the compound H2N—R4—NH2.

A preferred embodiment 29 concretizing any one of embodiments 23 to 28, wherein the reaction according to (i.2) is carried out at a temperature of the reaction mixture, preferably of the suspension as defined in embodiment 24 or 25, in the range of from 60 to 210° C., preferably in the range of from 150 to 200° C., at a pressure in the range of from 1 to 20 bar (100 to 2000 kPa), preferably in the range of from 1 to 16 bar (100 to 16000 kPa), more preferably the reaction according to (i.2) is carried out in a mixing apparatus, preferably in single or multishaft kneaders, more preferably in a kneaderlike reactor, a single- or multi-part/shaft kneader, an extruder, a paddle dryer, a mixer or a mill or in melt-mixing assemblies, more preferably in screw kneaders, such as single-screw kneaders and twin-screw kneaders.

A preferred embodiment 30 concretizing embodiment 29, wherein during the reaction according to (i.2) said temperature and said pressure are at least two of the following combinations of ranges: a temperature in the range of from 150 to 200° C. and a pressure in the range of from 9 to 13 bar (900 to 1300 kPa); a temperature in the range of from 170 to 190° C. and a pressure in the range of from 10 to 12 bar (1000 to 1200 kPa); a temperature in the range of from 80 to 120° C. and a pressure in the range of from 1 to 1.5 bar (100 to 150 kPa).

A preferred embodiment 31 concretizing any one of embodiments 23 to 30, further comprising (i.3) cooling the reaction mixture obtained from (i.2), preferably to a temperature of the mixture in the range of from 15 to 40° C., more preferably in the range of from 20 to 30° C.

A preferred embodiment 32 concretizing any one of embodiments 23 to 31, preferably of embodiment 29, further comprising (i.4) admixing the reaction mixture obtained from (i.2), preferably the cooled reaction mixture obtained from (i.3), with water and a suitable salt, and heating the obtained mixture, preferably to a temperature in the range of from 50 to 90° C., more preferably in the range of from 60 to 80° C., obtaining a suspension, wherein the suitable salt is potassium carbonate.

A preferred embodiment 33 concretizing any one of embodiments 23 to 32, further comprising (i.5) subjecting the mixture obtained from (i.2), preferably from (i.3), more preferably from (i.4), to solid-liquid separation, said solid-liquid separation preferably comprising one or more of centrifugation and filtration, more preferably filtration;

    • (i.6) washing the solids obtained from (i.5) with at least one suitable washing agent, said suitable washing agent preferably comprising water, more preferably comprising water and at least one suitable organic acid, wherein said at least one suitable organic acid, comprises, more preferably is, acetic acid and citric acid;
    • (i.7) drying the solids obtained from (i.6) in a gas atmosphere, said gas atmosphere preferably being one or more of nitrogen, air, and lean air and preferably having a temperature in the range of from 50 to 95° C., more preferably 60 to 90° C., more preferably 70 to 85° C.

A preferred embodiment 34 concretizing any one of embodiments 23 to 33, further comprising

    • (i) providing a mixture comprising the solid solution obtainable or obtained by a process of any one of embodiments 23 to 33, or providing a mixture comprising the solid solution of any one of embodiments 1 to 22, preferably providing a mixture comprising the solid solution obtainable or obtained from (1.2), more preferably from (i.3), more preferably from (i.4), more preferably from (i.5), more preferably from (i.6), more preferably from (i.7);
    • (ii) subjecting the mixture provided according to (i) to mechanical treatment;
    • (iii) adding water to the mixture obtained from (ii);
    • (iv) subjecting the mixture obtained from (iii) to solid-liquid separation;
    • (v) washing the solids obtained from (iv) with at least one suitable washing agent;
    • (vi) drying the solids obtained from (v), obtaining the solid solution.

A preferred embodiment 35 concretizing embodiment 34, wherein providing a mixture according to (i) comprises adding at least one suitable acid or solvent to the mixture, wherein the at least one suitable acid is preferably one or more of polyphosphoric acid and sulfuric acid, wherein more preferably, the at least one suitable acid comprises, more preferably is sulfuric acid, and wherein the at least one solvent comprises, preferably is water.

A preferred embodiment 36 concretizing any one of embodiment 34 or 35, wherein providing a mixture according to (i) is carried out at a temperature of the mixture in the range of from 30 to 120° C., preferably in the range of from 40 to 110° C., more preferably in the range of from 50 to 100° C.

A preferred embodiment 37 concretizing embodiment 34, wherein providing a mixture according to (i) is carried out at a temperature of the mixture in the range of from 30 to 80° C., preferably in the range of from 40 to 70° C., more preferably in the range of from 45 to 60° C., the process preferably further comprises adding at least one suitable base, solvent or sodium hydrosulfite to the mixture, wherein the at least one suitable base is preferably one or more of sodium hydroxide and potassium hydroxide, wherein more preferably, the at least one suitable base is sodium hydroxide, and wherein the at least one solvent comprises, preferably is water, more preferably wherein the process further comprises adding at least one suitable oxidant, wherein more preferably, the at least one suitable oxidant is one or more of oxygen or hydrogen peroxide.

A preferred embodiment 38 concretizing any one of embodiments 34 to 37, wherein the mechanical treatment according to (ii) comprises one or more kneading and milling, wherein kneading comprises coextrusion, salt kneading, single-shaft kneading and double-shaft kneading and wherein milling comprises wet milling, ball milling, bead milling, vibration milling, planetary milling and attritor milling.

A preferred embodiment 39 concretizing embodiment 38, wherein the mechanical treatment according to (ii) comprises, preferably is kneading, wherein said kneading is carried out at a temperature of the mixture in the range of from 40 to 120° C., preferably in the range of from 45 to 90° C., more preferably in the range of from 50 to 90° C., the process preferably further comprising, either directly before and/or during kneading, adding one or suitable solvent or one or more of sodium chloride, sodium sulfate and anhydrous aluminium sulfate, preferably sodium chloride to the mixture to be kneaded, wherein more preferably the weight ratio of one or more of sodium chloride, sodium sulfate and anhydrous aluminium sulfate relative to the mixture provided according to (i), is in the range of from 20:1 to 1:1, preferably 15:1 to 2:1, more preferably 10:1 to 2:1, more preferably 8:1 to 2:1, more preferably 6:1 to 2:1, and more preferably 4:1 to 2:1, and wherein the at least one solvent is preferably one or more ethylene glycol, diethylene glycol, diacetone alcohol, dimethylformamide, glycerine, triethylene glycol, dipropylene glycol, ethylene glycol monobutyl ether, methyl ethyl ketone, cyclohexanone, dimethylacetamide, N-methylpyrrolidone, butyl acetate, glycerol triacetate, sulfolane, xylene, tetrahydrofuran, butanol, water and dimethyl sulfoxide, wherein more preferably, the at least one solvent comprises, more preferably is diethylene glycol, diacetone alcohol, dimethylformamide, xylene, butanol, water and glycerine.

A preferred embodiment 40 concretizing embodiment 38 or 39, wherein the mechanical treatment according to (ii) further comprises, either directly before and/or during kneading, adding at least one or more of a synergist comprising sulfonic and carboxylic acid derivatives of perylene, indanthrone, phthalocyanine and diketopyrrolopyrrole, preferably in an amount of 1 to 15 weight-%, more preferably 1 to 5 weight-%, based on the total weight of the kneaded mixture, and/or a natural or synthetic resin comprising esters and salts of abietic acid, hydrated or hydrogenated or partially hydrogenated or dimerised rosin, preferably in an amount of 1 to 50 weight-%, more preferably 2 to 25 weight-%, based on the total weight of the kneaded mixture; or a polysorbate nonionic surfactant comprising an ester or a mixture of esters comprising lauric or sebacic acid comprising sorbitan monolaureate or dibutylsebacate polyoly, preferably in an amount of 1 to 50 weight-%, more preferably 2 to 20 weight-%, based on the total weight of the kneaded mixture, to the mixture to be kneaded.

A preferred embodiment 41 concretizing embodiment 38, wherein the mechanical treatment according to (ii) comprises, preferably is milling, wherein said milling is carried out at a temperature of the mixture in the range of from 40 to 120° C., preferably in the range of from 45 to 90° C., more preferably in the range of from 50 to 90° C., the process preferably further comprising, either directly before and/or during milling, adding one or more of sodium chloride, sodium sulfate and anhydrous aluminium sulfate, preferably sodium chloride to the mixture to be milled.

A preferred embodiment 42 concretizing embodiment 38 or 41, wherein the process further comprises, directly after milling, adding at least one suitable acid or solvent to the milled mixture under stirring at a temperature of the mixture in the range of from 40 to 200° C., preferably in the range of from 45 to 150° C., more preferably in the range of from 50 to 120° C., wherein the at least one suitable acid is preferably one or more of polyphosphoric acid and sulfuric acid, wherein more preferably, the at least one suitable acid comprises, more preferably is sulfuric acid, and wherein the at least one solvent is preferably one or more ethylene glycol, diethylene glycol, diacetone alcohol, dimethylformamide, glycerine, triethylene glycol, dipropylene glycol, ethylene glycol monobutyl ether, methyl ethyl ketone, cyclohexanone, dimethylacetamide, N-methylpyrrolidone, butyl acetate, glycerol triacetate, sulfolane, xylene, tetrahydrofuran, butanol, water and dimethyl sulfoxide, wherein more preferably, the at least one solvent comprises, more preferably is diethylene glycol, diacetone alcohol, dimethylformamide, xylene, tetrahydrofuran, butanol, water and glycerine.

A preferred embodiment 43 concretizing any one of embodiments 38 to 42, wherein milling is carried out with steel balls, silicon/aluminum/zirconium oxide beads, glass beads, ceramic beads and agate balls, preferably having a diameter in the range from 0.1 to 5 cm, and wherein milling is wet milling and wherein wet milling is carried out in water or in a mixture of water and at least one suitable organic solvent, and optionally at least one suitable base, wherein more preferably, the at least one suitable solvent comprises, more preferably is methanol, ethanol, propanol, isopropanol butanol, pentanol, ethylene glycol, diethylene glycol, triethylene glycol and dipropylene glycol, and wherein more preferably, the at least one suitable base comprises, more preferably is, sodium hydroxide, potassium hydroxide, sodium hydroxide, lithium hydroxide and benzyl trimethylammonium hydroxide.

A preferred embodiment 44 concretizing any one of embodiments 38 to 43, wherein the mechanical treatment according to (ii) further comprises, either directly before and/or during milling, adding one or more of a synergist, preferably in an amount of 1 to 15 weight-%, more preferably 1 to 5 weight-%, based on the total weight of the milled mixture, and/or a natural or synthetic resin comprising esters and salts of abietic acid, hydrated or partially hydrogenated or dimerised rosin, preferably in an amount of 1 to 50 weight-%, more preferably 5 to 30 weight-% based on the total weight of the milled mixture, and a natural rosin comprising derivative of abietic acid, preferably in an amount of 1 to 50 weight-%, more preferably 5 to 30 weight-%, based on the total weight of the milled mixture, to the mixture to be milled.

A preferred embodiment 45 concretizing any one of embodiments 38 to 44, wherein at least one or more of a synergist comprises sulfonic and carboxylic acid derivatives of perylene, indanthrone (PB 60), copper, aluminium or zinc phthalocyanine, quinacridone (PV 19, PR 202), dioxazine (PV 23, PV 37, PB 80) and diketopyrrolopyrrole (PR 254, PR 255).

A preferred embodiment 46 concretizing any one of embodiments 23 to 45, wherein the solid-liquid separation according to (iv) comprises one or more of centrifugation and filtration, more preferably filtration.

A preferred embodiment 47 concretizing any one of embodiments 23 to 46, wherein the at least one suitable washing agent according to (v) comprises, more preferably is water, wherein the solids obtained from (iv) are preferably washed until the water obtained from washing exhibits a conductivity of at most 100 microSiemens/cm.

A preferred embodiment 48 concretizing any one of embodiments 23 to 46, wherein drying the solids obtained from (v) is carried out in a gas atmosphere, said gas atmosphere preferably being one or more of nitrogen, air, and lean air and preferably having a temperature in the range of from 50 to 95° C., more preferably 60 to 90° C., more preferably 70 to 85° C.

A preferred embodiment 49 concretizing any one of embodiment 23 to 48, wherein n, X, R1, R2, R3, R4, X1 to X8 and specific combinations thereof are as defined in any one of embodiments 2 to 12.

A preferred embodiment 50 concretizing any one of embodiments 23 to 49, wherein the solid solution is the solid solution according to any one of embodiments 1 to 22.

According to embodiment 51 the present invention relates to solid solution, preferably a solid solution according to any one of embodiments 1 to 22, obtainable or obtained by a process according to any one of embodiments 23 to 49.

According to embodiment 52 the present invention relates to a solid solution according to any one of embodiments 1 to 22 or 51, comprised in one or more of a thermoplastic, elastomeric, crosslinked or inherently crosslinked polymer, preferably a polyolefin, polyamide, polyurethane, polyacrylate, polyacrylamide, polyvinyl alcohol, polycarbonate, polystyrene, polyester, polyacetal, a natural or synthetic rubber and a halogenated vinyl polymer in an amount from 0.01 weight-% to 70 weight-% based on the total weight of the polymer.

According to embodiment 53 the present invention relates to a solid solution according to any one of embodiments 1 to 22 or 51, comprised in one or more of a coating composition which is applied to the surface of the substrate, preferably a thermoplastic, elastomeric, crosslinked or inherently crosslinked polymer which is in the form of a film or coating applied to the surface of a substrate, or in the form of a fiber, sheet or other moulded or shaped article.

According to embodiment 54 the present invention relates to a solid solution according to any one of embodiments 1 to 22 or 51, comprised in one or more of a coating composition, a light detection and ranging (LiDAR) device, a near-infrared (NIR) non-absorbing component, a photovoltaic component, a heat management component, a thermal insulation component, a coloring paint, a printing ink, a recyclable plastic article, a biodegradable mulch, a toner, a charge-generating material, a color filter, a LC display and a security print component.

According to embodiment 55 the present invention relates to a solid solution according to any one of embodiments 1 to 22 or 51 for use as a component in one or more of a coating composition, a light detection and ranging (LiDAR) device, a near-infrared (NIR) non-absorbing component, a photovoltaic component, a heat management component, a thermal insulation component, a coloring paint, a printing ink, a recyclable plastic article, a biodegradable mulch, a toner, a charge-generating material, a color filter, a LC display and a security print component.

According to embodiment 56 the present invention relates to the use of a solid solution according to any one of embodiments 1 to 22 or 51 as a component of one or more of a coating composition, a light detection and ranging (LiDAR) device, a near-infrared (NIR) non-absorbing component, a photovoltaic component, a heat management component, a thermal insulation component, a coloring paint, a printing ink, a recyclable plastic article, a biodegradable mulch, a toner, a charge-generating material, a color filter, a LC display and a security print component.

According to embodiment 57 the present invention relates to a coating composition and/or a light detection and/or a ranging (LiDAR) device and/or a near-infrared (NIR) non-absorbing component and/or a photovoltaic component and/or a heat management component and/or a thermal insulation component and/or a coloring paint and/or a printing ink and/or a recyclable plastic article and/or a biodegradable mulch and/or a toner and/or a charge-generating material and/or a color filter and/or a LC display and/or a security print component, comprising a solid solution according to any one of embodiments 1 to 22 or 51.

According to embodiment 58 the present invention relates to a multilayer coating comprising: a primer coating comprising a solid solution according to any one of embodiments 1 to 22 or 51 and a white pigment in a weight ratio of from 1:99 to 99:1, preferably from 1:95 to 95:1; a basecoat comprising a black, preferably comprising a solid solution a solid solution according to any one of embodiments 1 to 22 or 51, colour, metallic or interference pigment; and optionally a clear topcoat.

According to embodiment 59 the present invention relates to the use of a solid solution according to any one of embodiments 1 to 22 or 51 for producing one or more of a coating composition, a light detection and ranging (LiDAR) device, a near-infrared (NIR) non-absorbing component, a near-infrared (NIR) non-absorbing component, a photovoltaic component, a heat management component, a thermal insulation component, coloring paint, a printing ink, a plastic, a recyclable plastic article, a biodegradable mulch, a toner, a charge-generating material, a color filter, a LC display and a security print component.

According to embodiment 60 the present invention relates to a method for producing one or more of a coating composition, a light detection and ranging (LiDAR) device, a near-infrared (NIR) non-absorbing component, a photovoltaic component, a heat management component, a thermal insulation component, a coloring paint, a printing ink, a plastic, a recyclable plastic article, a biodegradable mulch, a toner, charge-generating material, a color filter, a LC display and a security print component, the method comprising providing and processing a solid solution according to any one of embodiments 1 to 22 or 51.

According to embodiment 61 the present invention relates to a method for identifying an item, wherein said item comprises a mark comprising an effective amount of a solid solution according to any one of embodiments 1 to 22 or 51, wherein said mark is recorded under irradiation by electromagnetic waves of wavelength from 700 to 2000 nm, and the mark's image is used for identifying the item.

According to embodiment 62 the present invention relates to method for laser welding an article, wherein a solid solution according to any one of embodiments 1 to 22 or 51, is incorporated into a polymeric composition which is in contact with a surface of a meltable substrate containing a near infra-red absorbing material, then near infra-red radiation preferably from a laser of wavelength in the range from 700 to 2000 nm is passed through the layer containing the solid solution according to any one of embodiments 1 to 22 or 51 to the underlying substrate generating enough heat at the point of irradiation to melt together the two materials.

According to embodiment 63 the present invention relates to a method of identifying a recyclable plastic article comprising a solid solution according to any one of embodiments 1 to 22 or 51 with a laser signal of a wavelength in the range from 700 to 2000 nm.

According to embodiment 64 the present invention relates to the use of a solid solution according to any one of embodiments 1 to 22 or 51 as a near-infrared (NIR) transparent colorant which enables a significant signal to noise ratio in near-infrared (NIR) light detection.

According to embodiment 65 the present invention relates to the use of a solid solution according to any one of embodiments 1 to 22 or 51 for a LiDAR detection with a laser signal of a wavelength in the range from 700 to 2500 nm.

According to embodiment 66 the present invention relates to the use of a solid solution according to any one of embodiments 1 to 22 or 51 as a near-infrared (NIR) transparent black colorant in a near-infrared (NIR) non-absorbing component.

The present invention is further illustrated by the following Examples and Reference Examples.

EXAMPLES Sample Preparations

Sample Preparations 1 to 11 were prepared using solid solutions obtained in Example 1 below. The term “pigment” used in the following herein under refers to the solid solution according to the present invention which were prepared according to Example 1 below.

Sample Preparation 1: 20 Weight-% Pigment Millbase

A 20 weight-% pigment millbase was prepared by combining 20 weight-% of the pigment with 20 weight-% of a waterborne dispersant (Dispex® Ultra PX 4585 (50 weight-% dispersant and 50 weight-% water), an acrylic block copolymer supplied by BASF SE), 59.5 weight-% demineralised water and 0.5 weight-% antifoam additive (FoamStar® ST 2400 (100 weight-% defoamer) supplied by BASF SE) in a sealable container. Dispersion media (e.g. glass beads Ø 2 mm) were added to the container in the weight ratio 1:2 millbase components:beads and the container was sealed. The container was then loaded into a Skandex disperser (Skandex disperser is a well-known shaker disperser used extensively in the coatings industry. Similar designs are supplied by different companies of which LAU GmbH is one of the more popular suppliers) and the millbase components dispersed for 6 hrs. After dispersion, the beads were removed from the homogeneous liquid millbase by pouring the contents through a coarse filter. The resulting 20 weight-% pigment millbase was available for use in paint formulation.

Sample Preparation 2: 15 Weight-% Carbon Black Millbase

A 15 weight-% carbon black millbase was prepared by combining 15 weight-% of Colour Black FW200 carbon black pigment (supplied by Orion Engineered Carbons) with 15 weight-% of a waterborne dispersant (Dispex® Ultra PX 4585 (50 weight-%) dispersant and 50 weight-% water), an acrylic block copolymer supplied by BASF SE), 69.6 parts demineralised water and 0.4 weight-% antifoam additive (FoamStar® ST 2400 (100 weight-%) supplied by BASF SE) in a sealable container. Dispersion media (e.g. glass beads 02 mm) were added to the container in the weight ratio 1:2 millbase components:beads and the container sealed. The container was then loaded into a Skandex disperser and the millbase components dispersed for 6 hrs. After dispersion, the beads were removed from the homogeneous liquid millbase by pouring the contents through a coarse filter. The resultant 15 weight-% carbon black pigment millbase was available for use in paint formulation.

Sample Preparation 3: 70 Weight-% Pigment Titanium Dioxide Millbase

A 70 weight-% pigment millbase was prepared by combining 70 weight-% of Kronos 2310 titanium dioxide pigment (supplied by Kronos Worldwide Inc.) with 6.5 weight-% of a waterborne dispersant (Dispex® Ultra PX 4575 (40 weight-% dispersant and 60 weight-% water), an acrylic block copolymer supplied by BASF SE), 23.1 weight-% demineralised water and 0.4 weight-% antifoam additive (FoamStar© ST 2400 (100 weight-%) supplied by BASF SE) in a sealable container. Dispersion media (e.g. glass beads Ø 2 mm) were added to the container in the weight ratio 1:2 millbase components:beads and the container sealed. The container was then loaded into a Skandex disperser and the millbase components dispersed for 1 hr. After dispersion, the beads were removed from the homogeneous liquid millbase by pouring the contents through a coarse filter. The resultant 70 weight-% pigment millbase was available for use in paint formulation.

TABLE 1 Summary of different millbases (the numbers in the table are given in weight-%) Carbon Black Pigment Pigment Titanium Component Millbase Millbase Dioxide Millbase 1Carbon Black Pigment 15.0 — — 2Pigment — 20.0 — 3Titanium Dioxide Pigment — — 70.0 4Dispex ® Ultra PX 4585 15.0 20.0 — 5Dispex ® Ultra PX 4575 — — 6.5 Demineralised water 69.6 59.5 23.1 6FoamStar ® ST 2400 0.4 0.5 0.4 1Pigment Black 7 carbon black pigments are available commercially from various pigment companies e.g. Colour Black FW200, Orion Engineered Carbons 2Pigments according to Examples 1 to 2 3Pigment White 6 titanium dioxide pigments are available commercially from various pigment companies e.g. Kronos 2310, Kronos Worldwide Inc. 4Available commercially from BASF SE 5Available commercially from BASF SE 6Available commercially from BASF SE

Sample Preparation 4: Waterborne Basecoat Let-Down Resin

A waterborne let-down resin system was prepared by combining 15 weight-% alkali swellable acrylic dispersion (Setaqua® 6802 (24 weight-% solid resin material, 76 weight-% solvents and neutralising base) supplied by Allnex Resins), 9 weight-% thermosetting waterborne acrylic emulsion (Setaqua® 6160 (45 weight-% solid resin material, 55 weight-% volatile solvents and neutralising base) supplied by Allnex Resins), 52 weight-% aliphatic polyester based polyurethane emulsion (Daotan® TW 6466/36WA (36 weight-% solid resin material, 64 weight-% solvents and neutralising base) supplied by Allnex resins) and 4.8 weight-% of a methylated monomeric melamine crosslinker (Cymel® 303LF (>98 weight-% solid resin material, <2 weight-% volatile solvents and formaldehyde) supplied by Allnex Resins). Demineralised water, neutralising amine (dimethylethanolamine) and co-solvent (butyl glycol) were also incorporated to adjust the solids, viscosity and pH parameters of the let-down resin as used by somebody skilled in the art of waterborne resin system preparation.

Sample Preparation 5: Aluminium Base

7.6 weight-% Toyal TCR 3040 silver dollar, non-leafing aluminium paste (supplied by Toyo Aluminium) was wetted out with 2 weight-% Additol® XL250 pigment wetting agent (55 weight-% solid and 45 weight-% volatile components including solvents) supplied by Allnex Resins) and 11 weight-% hydrophilic solvents (n-butanol and butyl glycol). Once fully wetted out and homogeneous, 50 weight-% waterborne basecoat let-down resin (Sample Preparation 4) was added under stirring followed by 29.4 weight-% demineralised water.

Sample Preparation 6: Pigment Masstone Basecoat (2.5 Weight-% Pigment)

12.5 weight-% of the 20 weight-% pigment millbase (Sample Preparation 1) were combined under stirring with 60 weight-% of the Waterborne Basecoat Let-down resin (Sample Preparation 4) and other co-solvent and application additives (e.g. wetting agent) known to those skilled in the art of waterborne coatings preparation. Viscosity and pH adjustment are achieved using a combination of demineralised water, neutralised Rheovis® AS 1130 (30 weight-% alkali swellable acrylic copolymer emulsion (ASE) in water, supplied BASF SE) and neutralising amine (dimethylethanolamine) to achieve a viscosity of 40-45 secs DIN4 flow cup and a pH in the range 8.0 to 8.5.

Sample Preparation 7: Carbon Black Masstone Basecoat (2.5 Weight-% Pigment)

16.7 weight-% of the 15 weight-% Carbon Black millbase (Sample Preparation 2) were combined under stirring with 60 weight-% of the Waterborne Basecoat Let-down resin (Sample Preparation 4) and other co-solvent and application additives (e.g. wetting agent) known to those skilled in the art of waterborne coatings preparation. Viscosity and pH adjustment are achieved using a combination of demineralised water, neutralised Rheovis® AS 1130 (30 weight-% alkali swellable acrylic copolymer emulsion (ASE) in water, supplied BASF SE) and neutralising amine (dimethylethanolamine) to achieve a viscosity of 40-45 secs DIN4 flow cup and a pH in the range 8.0 to 8.5.

TABLE 2 Summary of different masstone basecoats (the numbers in the table are given in weight-%) Pigment Carbon Black Masstone Masstone Component Basecoat Basecoat Waterborne Basecoat Let-down resin 60.0 60.0 Carbon Black Millbase — 16.7 Pigment Millbase 12.5 — 1Wetting agent solution 1.3 1.3 2Organic solvents 2.5 2.5 Demineralised water 13.7 12.9 3Rheology and pH adjustment 10.0 6.6 1Wetting agent solution comprising Surfynol ® 104 (100 weight-% defoamer, supplied by Evonik in butyl glycol 2Blend of alcohol and glycol ether solvents to achieve good film coalescence 3Viscosity and pH adjustment are achieved using a combination of demineralised water, neutralised Rheovis ® AS 1130 (30 weight-% alkali swellable acrylic copolymer emulsion (ASE) in water, supplied BASF SE) and a neutralising amine (dimethylethanolamine) Solids content 23.3 weight-% Pigment content 2.5 weight-% Pigment:Binder weight ratio 1:8.3

Sample Preparation 8: 10:90 (weight ratio) Pigment:Titanium Dioxide White Reduction

10.1 weight-% of the 20 weight-% pigment millbase (Preparation 1) and 25.8 weight-% pigment titanium dioxide millbase (Preparation 3) were combined under stirring with 50.7 weight-% of the Waterborne Basecoat Let-down resin (Sample Preparation 4) and other co-solvent and application additives (e.g. wetting agent) known to those skilled in the art of waterborne coatings preparation. Viscosity and pH adjustment are achieved using a combination of demineralised water, neutralised Rheovis® AS 1130 (30 weight-% alkali swellable acrylic copolymer emulsion (ASE) in water, supplied BASF) and neutralising amine (dimethylethanolamine) to achieve a viscosity of 40-45 secs DIN4 flow cup and a pH in the range 8.0 to 8.5.

TABLE 3 Summary of different white reductions (the numbers in the table are given in weight-%) 10:90 10:90 Carbon Pigment:White Black:White Component Reduction Reduction Waterborne Basecoat Let-down resin 50.7 50.7 Carbon Black Millbase — 13.4 Pigment Millbase 10.1 — Titanium Dioxide Millbase 25.8 25.8 1Wetting agent solution 0.9 0.9 2Organic solvents 2.5 2.5 Demineralised water 5.0 1.7 3Rheology and pH adjustment 5.0 5.0 1Wetting agent solution comprising Surfynol ® 104 (100 weight-% defoamer, supplied by Evonik in butyl glycol 2Blend of alcohol and glycol ether solvents to achieve good film coalescence 3Viscosity and pH adjustment are achieved using a combination of demineralised water, neutralised Rheovis ® AS 1130 (30 weight-% alkali swellable acrylic copolymer emulsion (ASE) in water, supplied BASF SE) and a neutralising amine (dimethylethanolamine) Solids content 38.2 weight-% Pigment content 20.1 weight-% (10:90 Black:Titanium dioxide) Pigment:Binder weight ratio 1:0.9

Sample Preparation 9: 50:50 (Weight Ratio) Pigment:Aluminium Reduction

28.3 weight-% of the Aluminium Base (Sample Preparation 5) were combined with 45.0 weight-% Waterborne Basecoat Let-down Resin (Sample Preparation 4) under stirring. Demineralised water, neutralising amine and co-solvent were added to adjust the solids and pH of the mixture. 8.5 weight-% of the 20 weight-% pigment millbase were added under stirring. Flake orientation in the basecoat was controlled using a Laponite© RD (clay type rheology based additive, supplied by Byk-Chemie GmbH). Final spray viscosity and pH adjustment are achieved using a combination of demineralised water, neutralised Rheovis® AS 1130 (30 weight-% alkali swellable acrylic copolymer emulsion (ASE) in water, supplied BASF) and neutralising amine (dimethylethanolamine) to achieve a viscosity of 40-45 secs DIN4 flow cup and a pH in the range 8.0 to 8.5.

TABLE 4 Summary of different aluminium reductions (the numbers in the table are given in weight-%) 50:50 50:50 Carbon Pigment:Aluminium Black:Aluminium Component Reduction Reduction Waterborne Basecoat Let-down 45.0 45.0 resin Carbon Black Millbase — 11.3 Pigment Millbase 8.5 — Aluminium Base 28.3 28.3 1Surfactant solution 0.9 0.9 2Flake orientation additive 3.5 3.5 Demineralised water 5.8 3.0 3Rheology and pH adjustment 8.0 8.0 1Wetting agent solution comprising Surfynol ® 104 supplied by Evonik in butyl glycol 2Flake control additive comprising clay type additive e.g. Laponite ® RD supplied by BYK-Chemie GmbH, a low molecular weight polypropylene glycol e.g. Pluriol ® P900 supplied by BASF SE and demineralised water 3Viscosity and pH adjustment are achieved using a combination of demineralised water, neutralised Rheovis ® AS 1130 (alkali swellable acrylic copolymer emulsion (ASE) in water, supplied BASF SE) and a neutralising amine (dimethylethanolamine) Solids content 23.7 weight-% Pigment content 3.4 weight-% (50:50 weight-% Pigment:Aluminium flake) Pigment:Binder weight ratio 1:5.7

Sample Preparation 10: 0.2 Weight-% Pigment Masstone in a Polyvinyl Chloride (PVC) Film

A polyvinyl chloride (PVC) film of thickness of ˜0.3 mm is produced on a twin-roll mill at 150° C. containing 0.2 weight-% of the pigment in a full shade application.

PVC grade: SorVyl DB 2105 transparent from Polymer-Chemie DE. Two roll mill type Collin 150 (Collin Lab & Pilot Solutions) with total milling time: ca. 10 min.

Sample Preparation 11: 1:10 Weight-% Pigment:Titanium Dioxide Reduction in a Polyvinyl Chloride (PVC) Film

A polyvinyl chloride (PVC) film of thickness of ˜0.3 mm is produced on a twin-roll mill at 150° C. containing 0.5 weight-% of the pigment and 5 weight-% TiO2 for a white reduction application (i.e., yielding a 1:10 TiO2 reduction).

PVC grade: SorVyl DB 2105 transparent from Polymer-Chemie DE. Two roll mill type Collin 150 (Collin Lab & Pilot Solutions) with total milling time: ca. 10 min.

REFERENCE EXAMPLES: DETERMINATION METHODS a) L*a*b*C*h Coloristic Determination

The term L* (lightness) used herein means the lightness in the L*a*b* color space (also referred to as CIELAB) specified by the Commission Internationale de l'Eclairage, wherein a* and b* are the chromaticity coordinates. The L* value is measured at an observation angle of 25°. According to the CIELAB system, L*=100 means the lightest value (white), L*=0 means the darkest value (black). Generally, a L* value refers to an opaque coating.

The term C* (chrome) used herein means the chroma in the L*C*h color space (also referred to as CIELAB) specified by the Commission Internationale de l'Eclairage, wherein L* is the same lightness as in the L*a*b* color space and h is the hue angle.

Solid colors (CIELAB color measurement) were measured using Datacolor 650 d8 integrating sphere spectrophotometer with D65 illuminant and 10° observer. Data handling via BASF ColorCare software.

Effect colors (CIELAB color measurement) were measured using BYK-mac 6 angle spectrophotometer (−15°, 15°, 25°, 45°, 75° and 110°) with D65 illuminant and 10° observer. Data handling via BASF ColorCare software.

b) NIR Reflectance Determination-Total Solar Reflectance (TSR) and Specified NIR Wavelengths (905 nm and 1550 nm)

The term TSR used herein means Total Solar Reflectance and is a measurement of surface reflective capability of an object in the wavelength range 300-2500 nm.

NIR reflectances at 905 nm and 1550 nm are seen as being representative of NIR wavelengths used in LiDAR based autonomous driving applications.

TSR and the specified NIR wavelengths were measured using an Agilent Cary 5000 UV-Vis-NIR Spectrophotometer. The TSR was measured according to ASTM Standard Method E 903-96 using the direct normal solar spectral irradiance from ASTM G159-98.

c) XRD

X-ray diffraction was determined with a multiple sample changer operating in Bragg-Brentano geometry and equipped with a Lynx-Eye detector. Bruker D8 Advance XDR 2 was used. Primary side: Cu-anode, divergence slit set to 0.1°, air-scatter-shield in place; Secondary side: Air scatter slit 8 mm with a 0.5 mm Ni-absorption filter, 4° sollers, Lynx-Eye detector set to an opening angle of 3°. The sample was filled into the sample holder and smoothed with a glass slide.

D) Masstone, Titanium Dioxide Reduction and Aluminium Reduction Test Panels

All basecoat samples were spray applied onto unprimed Q-panel aluminium test panels using an automatic HVLP spray gun (High Volume Low Pressure, e.g. SATA LP90), mounted on an Intec laboratory spray robot. The basecoat layer was dried for 15 min at 80° C. Effective Metal Temperature (EMT). The basecoat was applied to a layer thickness where opacity was achieved (typical dry film thicknesses: Masstone 15-20 microns; 10:90 weight-% Pigment:TiO2 reduction 30-35 microns; 50:50 weight-% Pigment:Al reduction 15-20 microns). A typical one component acrylic melamine based clearcoat, which contains a combination of UV absorber (e.g. Tinuvin® 400 (100% hydroxyphenyltriazine UV absorber), supplied by BASF SE) and hindered amine light stabilizer (HALS) (e.g. Tinuvin® 123 (100 weight-%) supplied by BASF SE), was then spray applied over the dried basecoat layer. After a rest time at ambient temperature to allow for solvent evaporation, the panels were baked for 30 min at 140° C. EMT. A dry film thickness of 35-40 microns clearcoat was applied.

These basecoat panels were used for colorimetry and accelerated weathering testing.

e) Masstone Test Panels for UV-Vis-NIR Spectroscopy

The 2.5 weight-% masstone basecoat samples (Sample Preparation 6) were applied onto Leneta opacity chart form 2A using a 150 micron wire wound applicator bar mounted on a Zehntner ZAA2300 automatic film applicator. After a rest time at ambient temperature to allow for solvent evaporation, the panels were dried for 30 min at 80° C. A dry film thickness of 20-25 microns was applied. A typical one component acrylic melamine based clearcoat, which contains a combination of UV absorber (e.g. Tinuvin® 400 (100 weight-% hydroxyphenyltriazine UV absorber), supplied by BASF SE) and hindered amine light stabilizer (HALS) (e.g. Tinuvin® 123 (100 weight-%) supplied by BASF SE), was then applied using a 100 micron wire wound applicator bar mounted on a Zehntner ZAA2300 automatic film applicator over the dried basecoat layer. After a rest time at ambient temperature to allow for solvent evaporation, the panels were baked for 30 min at 140° C. EMT. A dry film thickness of 35-40 microns clearcoat was applied.

These masstone panels were also used for colorimetry.

f) UV-Vis-NIR (Near-Infrared Reflectance) Data

UV-Vis-NIR (near-infrared reflectance) data have been obtained using a spectrophotometer that measures the reflection/transmission characteristics of a sample across the UV, visible and NIR parts of the electromagnetic spectrum. UV-Vis-NIR data has been determined using an Agilent Cary 5000.

g) Particle Size

The particle size has been determined using transmission electron microscopy (TEM). A very small amount of the sample powder is transferred from the tip of a microspatula to a glass slide. It is wetted with 5 drops of ethanol and rubbed between another glass slide in order to distribute the pigment homogeneously. A carbon coated TEM grid (SF 162) is flat-dipped on the coated slide. After short drying in air the sample is then examined in a Zeiss Libra 120 transmission electron microscope, which is equipped with an omega filter operated at 120 kV in elastic light field mode at various magnifications at representative positions.

h) Coloristic Measurement of the 0.2 Weight-% Pigment Masstone in a PVC Film

The colorimetric measurement of the 0.2 weight-% pigment masstone (Sample Preparation 10) and standard in a full shade application is carried out over white using the spectral method ISO 18314-1 (2015) with d/8°- or 8°/d geometry using a gloss trap. Test characteristics are measured according to ISO 11664-4 (2008; 18314-2 (2015) for light a source D65 and 10° standard observer over a white substrate.

i) Coloristic Measurement of the 1:10 TiO2-Pigment:Titanium Dioxide Reduction in a PVC Film

The colorimetric measurement of the 1:10 TiO2 white reduction (Sample Preparation 11) and standard is carried out using the spectral method (ISO 18314-1 (2015)) with 30°/30° measurement geometry. After color strength adjustment, the test characteristics are measured according to ISO 11664 4 (2008; 18314-2 (2015)) for light source D65 and 10° standard observer.

Examples 1-3: Preparation of the Solid Solution Starting from Compound IV

TABLE 5 Overview of solid solution starting from compound IV Amine 1 Amine 2 R1—NH2 H2N—R3—NH2 Amine 1/Amine 2 Examples R2—NH2 H2N—R4—NH2 weight-% Example 1 p-methoxybenzylamine o-phenylenediamine 80/20 Example 2 p-methoxybenzylamine o-phenylenediamine 85/15 Example 3 p-methoxybenzylamine 4,5-dichloro-o-phenelynediamine 80/20

Example 1

An autoclave with a capacity of 1 litre was charged with 130 g perylene bisanhydride (0.169 mol) as a water-moist presscake containing 51% by weight of perylene bisanhydride, 350 g water and 12.8 g (0.148 mol) piperazine. After adding 36.4 g (0.265 mol) p-methoxybenzylamine and 7.5 g (0.069 mol) 1,2-diaminobenzene (o-phenylenediamine), the reaction suspension was heated to 180° C. and was hold for 25 h at a pressure of 11 bar. After cooling, 600 mL water and 33.8 g of potassium carbonate were added and the reaction mixture was heated to 70° C. The suspension was filtered and washed successively with 3500 mL water, 3500 mL 10% citric acid and 3500 mL water. Drying at 80° C. afforded 102.7 g of the solid solution, corresponding to 99.3% of the theory as a black powder. The pigment is pulverized in a mill and the coloristic is evaluated in WB coating system. A millbase containing Example 1 only was prepared according to Sample Preparation 1. A comparative 2.5 weight-% Pigment Masstone containing Example 1 only was prepared according to Sample Preparation 6. A comparative 10:90 (weight ratio) Example 1:Titanium Dioxide Reduction prepared according to Sample Preparation 8. A comparative 50:50 (weight ratio) Example 1:Aluminium Reduction was prepared according to Sample Preparation 9. XRD see FIG. 1.

Example 2

An autoclave with a capacity of 1 litre was charged with 170 g (0.221 mol) of perylene bisanhydride as water-moist presscake containing 51% by weight of perylene bisanhydride, 450 g water and 16.8 g (0.195 mol) piperazine. After adding 50.5 g (0.368 mol) p-methoxybenzylamine and 7.4 g (0.068 mol) 1,2-diaminobenzene (o-phenylenediamine), the reaction suspension was heated to 180° C. and was hold for 25 h at a pressure of 11 bar. After cooling, 600 mL of water and 41.6 g of potassium carbonate were added and the reaction mixture was heated to 70° C. The suspension was filtered and washed successively with 4000 mL water, 4000 mL 10 weight-% citric acid and 4000 mL water. Drying at 80° C. afforded 134 g pigment as a black powder, corresponding to 98.3% of the theory. The pigment is pulverized in a mill and the coloristic is evaluated in WB coating system. A millbase containing Example 2 only was prepared according to Sample Preparation 1. A comparative 2.5 weight-% Pigment Masstone containing Example 2 only was prepared according to Sample Preparation 6. A comparative 10:90 (weight ratio) Example 2:Titanium Dioxide Reduction prepared according to Sample Preparation 8. A comparative 50:50 (weight ratio) Example 2:Aluminium Reduction was prepared according to Sample Preparation 9.XRD see FIG. 2.

Example 3

An autoclave with a capacity of 1 litre was charged with 130 g (0.169 mol) of perylene bisanhydride as water-moist presscake containing 51% by weight of perylene bisanhydride, 430 g water and 12.8 g (0.149 mol) piperazine. After adding 36.4 g (0.265 mol) p-methoxybenzylamine and 12.6 g (0.071 mol) 1,2-diamino-4,5-dichloro-benzene, the reaction suspension was heated to 180° C. and was hold for 25 h at a pressure of 11 bar. After cooling, 600 mL of water and 33.8 g of potassium carbonate were added and the reaction mixture was heated to 70° C. The suspension was filtered and washed successively with 3500 mL water, 233 g of 10 weight-% citric acid and 1200 mL water. Drying at 80° C. afforded 105 g pigment as a black powder, corresponding to 99% of the theory. The pigment is pulverized in a mill and the coloristic is evaluated in WB coating system. A millbase containing Example 4 only was prepared according to Sample Preparation 1. A comparative 2.5 weight-% Pigment Masstone containing Example 4 only was prepared according to Sample Preparation 6. A comparative 10:90 (weight ratio) Example 4:Titanium Dioxide Reduction prepared according to Sample Preparation 8. A comparative 50:50 (weight ratio) Example 4:Aluminium Reduction was prepared according to Sample Preparation 9. XRD see FIG. 3.

Example 4

A kneading apparatus (Z-blade kneader) with capacity of 1.1 litre is charged with 33.4 g of solid solution pigment from Example 1 (90 weight-%) and 3.47 g of Staybelite resin (10 weight-%). Sodium chloride 222 g and 60 g of diacetone alcohol (DAA) added to the kneader and the rotary speed is set at 100 rpm. The walls of the apparatus are thermostated at 85° C. After 8 hours of kneading at 85° C. the kneading is stopped. To kneading mass added water 1500 g. The mixture is filtered off until the conductivity of the filtrate is below <100 μS/cm. The wet presscake dried in oven at 80° C. for 24 h. The yield of black pigment 35.8 g. The pigment is pulverized in a mill and the coloristic is evaluated in WB coating system. A millbase containing Example 5 only was prepared according to Sample Preparation 1. A comparative 2.5 weight-% Pigment Masstone containing Example 5 only was prepared according to Sample Preparation 6. A comparative 10:90 (weight ratio) Example 5:Titanium Dioxide Reduction prepared according to Sample Preparation 8. A comparative 50:50 (weight ratio) Example 5:Aluminium Reduction was prepared according to Sample Preparation 9. XRD see FIG. 4.

Example 5

A kneading apparatus (Z-blade kneader) with capacity of 1.1 litre was charged with 26 g of solid solution pigment of Example 2 (90 weight-%) and 2.9 g of Staybelite resin (10 weight-%). 231 g sodium chloride and 58 g diethylene glycol (DEG) were added to the kneader and the rotary speed was set at 100 rpm. The walls of the apparatus were thermostated at 115° C. After 8 hours of kneading at 115° C., the kneading was stopped. Then, to the kneading mass 1500 g water was added. The mixture was then filtered off until the conductivity of the filtrate was below 100 μS/cm. The wet presscake was dried in an oven at 80° C. for 24 h. The obtained solid solution was pulverized in a mill. The yield of the obtained solid solution was 25.4 g. The pigment is pulverized in a mill and the coloristic is evaluated in WB coating system. A millbase containing Example 6 only was prepared according to Sample Preparation 1. A comparative 2.5 weight-% Pigment Masstone containing Example 6 only was prepared according to Sample Preparation 6. A comparative 10:90 (weight ratio) Example 6:Titanium Dioxide Reduction prepared according to Sample Preparation 8. A comparative 50:50 (weight ratio) Example 6:Aluminium Reduction was prepared according to Sample Preparation 9. XRD see FIG. 5.

Example 6

A kneading apparatus (Z-blade kneader) with capacity of 1.1 litre was charged with 33.4 g of solid solution pigment of Example 1 (90 weight-%) and 3.7 g of Staybelite resin (10 weight-%). 222 g sodium chloride and 58 g diethylene glycol (DEG) were added to the kneader and the rotary speed was set at 100 rpm. The walls of the apparatus were thermostated at 115° C. After 8 hours of kneading at 100° C., the kneading was stopped. Then, to the kneading mass 1500 g water was added. The mixture was then filtered off until the conductivity of the filtrate was below 100 μS/cm. The wet presscake was dried in an oven at 80° C. for 24 h. The obtained solid solution was pulverized in a mill. The yield of the obtained solid solution was 35.6 g. The pigment is pulverized in a mill and the coloristic is evaluated in WB coating system. A millbase containing Example 7 only was prepared according to Sample Preparation 1. A comparative 2.5 weight-% Pigment Masstone containing Example 7 only was prepared according to Sample Preparation 6. A comparative 10:90 (weight ratio) Example 7:Titanium Dioxide Reduction prepared according to Sample Preparation 8. A comparative 50:50 (weight ratio) Example 7:Aluminium Reduction was prepared according to Sample Preparation 9. XRD see FIG. 6.

Example 7

A kneading apparatus (Z-blade kneader) with capacity of 1.1 litre is charged with 33.4 g. of solid solution pigment from Example 2 (90 weight-%) and 3.47 g of Staybelite resin (10 weight-%). Sodium chloride 222 g and 60 g of diacetone alcohol (DAA) added to the kneader and the rotary speed is set at 100 rpm. The walls of the apparatus are thermostated at 90° C. After 8 hours of kneading at 90° C. the kneading is stopped. To kneading mass added water 1500 g. The mixture is filtered off until the conductivity of the filtrate is below <100 μS/cm. The wet presscake dried in oven at 80° C. for 24 h. The yield of black pigment 34.0 g. The pigment is pulverized in a mill and the coloristic is evaluated in WB coating system. A millbase containing Example 8 only was prepared according to Sample Preparation 1. A comparative 2.5 weight-% Pigment Masstone containing Example 8 only was prepared according to Sample Preparation 6. A comparative 10:90 (weight ratio) Example 8:Titanium Dioxide Reduction prepared according to Sample Preparation 8. A comparative 50:50 (weight ratio) Example 8:Aluminium Reduction was prepared according to Sample Preparation 9. XRD see FIG. 7.

Example 8

A kneading apparatus (Z-blade kneader) with a capacity of 1.1 litre was charged with 37.1 g of solid solution pigment from Example 3. 222 g sodium chloride and 60 g of diacetone alcohol (DAA) were added to the kneader and the rotary speed was set at 100 rpm. The walls of the apparatus were thermostated at 65° C. After 8 hours of kneading, the kneading was stopped. Then, 1500 g of water was added to the kneading mass. The mixture was filtered off until the conductivity of the filtrate was below 100 μS/cm. The wet presscake was dried in an oven at 80° C. for 24 h. The obtained material was pulverized in a mill. The yield of the obtained solid solution was 36 g. The pigment is pulverized in a mill and the coloristic is evaluated in WB coating system. A millbase containing Example 10 only was prepared according to Sample Preparation 1. A comparative 2.5 weight-% Pigment Masstone containing Example 10 only was prepared according to Sample Preparation 6. A comparative 10:90 (weight ratio) Example 10:Titanium Dioxide Reduction prepared according to Sample Preparation 8. A comparative 50:50 (weight ratio) Example 10:Aluminium Reduction was prepared according to Sample Preparation 9. XRD see FIG. 8.

Example 9

A kneading apparatus (Z-blade kneader) with a capacity of 1.1 litre was charged with 37.1 g of solid solution pigment from Example 1. 222 g sodium chloride and 62 g of diacetone alcohol (DAA) were added to the kneader and the rotary speed was set at 100 rpm. The walls of the apparatus were thermostated at 65° C. After 8 hours of kneading, the kneading was stopped. Then, 1500 g of water was added to the kneading mass. The mixture was filtered off until the conductivity of the filtrate was below 100 μS/cm. The wet presscake was dried in an oven at 80° C. for 24 h. The obtained material was pulverized in a mill. The yield of the obtained solid solution was 35 g. The pigment is pulverized in a mill and the coloristic is evaluated in WB coating system. A millbase containing Example 11 only was prepared according to Sample Preparation 1. A comparative 2.5 weight-% Pigment Masstone containing Example 11 only was prepared according to Sample Preparation 6. A comparative 10:90 (weight ratio) Example 11:Titanium Dioxide Reduction prepared according to Sample Preparation 8. A comparative 50:50 (weight ratio) Example 11:Aluminium Reduction was prepared according to Sample Preparation 9. XRD see FIG. 9.

Example 10

A kneading apparatus (Z-blade kneader) with a capacity of 1.1 litre was charged with 33.4 g of solid solution pigment from Example 3 (90 weight-%) and 3.7 g of Staybelite resin (10 weight-%). 222 g sodium chloride and 61 g of diacetone alcohol (DAA) were added to the kneader and the rotary speed was set at 100 rpm. The walls of the apparatus were thermostated at 90° C. After 6 hours of kneading at 90° C., the kneading was stopped. Then, 1500 g of water was added to the kneading mass. The mixture was filtered off and washed with water until the conductivity of the filtrate was below <100 μS/cm. The wet presscake was dried in a vacuum oven at 60° C. and 50 mbar for 24 hours. The obtained material was pulverized in a mill and the coloristic properties were evaluated in a PVC film.

The pigment masstone and white reduction in a PVC film were prepared according to Sample Preparation 10 and 11, respectively.

COMPARATIVE EXAMPLES

Comparative Example 1 was synthesized according to U.S. Pat. No. 4,450,273, Example 1 and represents Spectrasense™ (Paliogen®) Black L 0086, wherein R—NH2 and R2—NH2 are p-methoxybenzylamine.

Comparative Example 1 represents the single Compound 1 (Spectrasense™ Black L 0086 supplied by BASF Colors and Effects). A comparative millbase containing Compound 2 only was prepared according to Sample Preparation 1. A comparative 2.5 weight-% Pigment Masstone containing Compound 1 only was prepared according to Sample Preparation 6. A comparative 10:90 (weight ratio) Compound 1:Titanium Dioxide Reduction prepared according to Sample Preparation 8. A comparative 50:50 (weight ratio) Compound 1:Aluminium Reduction was prepared according to Sample Preparation 9.

Comparative Example 2 was synthesized according to US 2010/0184983 A1, Example 1 and represents Spectrasense™ (Lumogen®) Black K 0087, wherein H2N—R3—NH2 and H2N—R4—NH2 are o-phenylenediamine.

Comparative Example 2 represents the single Compound 2 (Spectrasense™ Black K 0087 supplied by BASF Colors and Effects). A comparative millbase containing Compound 2 only was prepared according to Sample Preparation 1. A comparative 2.5 weight-% Pigment Masstone containing Compound 2 only was prepared according to Sample Preparation 6. A comparative 10:90 (weight ratio) Compound 2:Titanium Dioxide Reduction prepared according to Sample Preparation 8. A comparative 50:50 (weight ratio) Compound 2:Aluminium Reduction was prepared according to Sample Preparation 9.

Comparative Example 3 represents carbon black (Pigment Black 7, PBK-7, Colour Black FW200, supplied by Orion Engineered Carbons). A comparative millbase containing carbon black only was prepared according to Sample Preparation 2. A comparative 2.5 weight-% Pigment Masstone containing carbon black (Pigment Black 7) only was prepared according to Sample Preparation 7.

TABLE 6 CIELAB panel data of a 2.5 weight-% Pigment Masstone prepared according to Sample Preparation 6 over white Colour Position [SPEX 0.00 d8, over White] h C* L* a* b* Comparative Example 1 117.0 1.8 5.5 −0.8 1.6 Comparative Example 2 75.8 6.6 7.8 1.6 6.4 Example 3 89.6 5.5 7.3 0.0 5.5 Example 4 88.5 5.2 5.1 0.1 5.2 Example 5 77.3 2.6 3.1 0.6 2.6 Example 6 91.2 5.1 4.6 −0.1 5.1 Example 7 92.3 6.7 6.0 −0.3 6.7

TABLE 7 CIELAB panel data of a 10:90 weight-% Pigment:Titanium Dioxide Reduction prepared according to Sample Preparation 8 Colour Position [SPIN 0.04 d8] Strength Adjusted h C* L* a* b* Comparative Example 1 207.3 6.9 51.4 −6.1 −3.1 Comparative Example 2 294.5 22.0 52.2 9.1 −20.0 Example 3 269.9 7.5 50.3 0.0 −7.5 Example 4 270.7 8.0 50.4 0.1 −8.0 Example 5 262.7 7.2 50.6 −0.9 −7.2 Example 6 266.5 7.8 50.6 −0.5 −7.7 Example 7 265.7 6.4 50.2 −0.5 −6.4

From the above, by careful consideration of the chemical composition of the pigment and the processing conditions used, solid solution pigments can be prepared. The individual pigments can be seen to display highly desirable neutral black (masstone) or neutral (or slightly bluish) grey (reduction) coloristic properties, characterized by low a* and b* values compared to existing, available, single component, black perylene pigments of Comparative Examples.

TABLE 8 CIELAB panel data of a 50:50 weight-% Pigment:Aluminium Reduction prepared according to Sample Preparation 9 h C* L* a* b* Colour Position [SPEX 0.00 −15°] Comparative Example 1 124.0 16.0 101.0 −8.9 13.2 Comparative Example 2 308.9 41.8 69.2 26.3 −32.6 Example 3 23.5 7.1 85.7 6.5 2.8 Example 4 4.3 9.0 83.3 9.0 0.7 Example 5 16.2 6.9 84.1 6.6 1.9 Example 6 14.2 7.5 79.3 7.3 1.8 Example 7 26.9 10.0 87.0 8.9 4.5 Colour Position [SPEX 0.00 110°] Comparative Example 1 106.4 4.3 11.7 −1.2 4.1 Comparative Example 2 2.7 4.8 10.7 4.8 0.2 Example 3 85.2 5.3 11.5 0.4 5.3 Example 4 81.0 6.5 10.7 1.0 6.4 Example 5 77.1 5.6 9.9 1.2 5.4 Example 6 85.2 6.2 10.0 0.5 6.2 Example 7 84.0 7.6 12.8 0.8 7.6

From the above, by careful consideration of the chemical composition of the pigment and the processing conditions used, solid solution pigments can be prepared. The individual pigments can be seen to display highly desirable neutral grey (1:1 reduction with aluminium) coloristic properties, characterized by low a* and b* values compared to existing, available, single component, perylene black pigments.

Example 3, Examples 4, 5 and 6 (based on Example 1) and Example 7 (based on Example 2) prepared using appropriate processing methods, display neutral black/grey coloristics from a single solid solution pigment.

The solid solution pigments described, when dispersed into a binder system e.g. for use in a coating, will behave as a single pigment providing predictable neutral coloristics at all concentrations, based on the weight content of the pigment in the formulation. Existing commercial single component perylene black pigments (symmetrical substituents) need to be blended with other pigments in order to achieve similar neutral coloristics. This requirement for an additional shading pigment leads to practical complexities in execution as the coloristic obtained from the dispersed mixed pigments can vary significantly according the dispersion conditions used and the required tint level in the target color. In order to achieve the required coloristic at all concentrations, generally the ratios of the blended components need to be adjusted to achieve the same neutral coloristic.

TABLE 9 NIR reflectance data over a white reflective substrate (>90% reflectance) at 905 nm and over a white reflective substrate (>70% reflectance) at 1550 nm 905 nm % 1550 nm % Examples Over White Over White Comparative Example 1 87.0 72.3 Comparative Example 2 70.9 70.5 Comparative Example 3 4.2 4.1 Example 3 81.0 70.1 Example 4 77.3 71.4 Example 5 76.8 72.2 Example 6 77.4 71.2 Example 7 76.2 71.8

From the above, by careful consideration of the chemical composition of the pigment and the processing conditions used, solid solution pigments can be prepared. The individual inventive solid solution pigments can be seen to display highly desirable NIR non-absorbing properties, characterized by very high NIR reflectance values comparable to existing, available, single component, black perylene pigments of Comparative Examples.

TABLE 10 NIR reflectance data over a white reflective substrate (>90% reflectance) at 905 nm and over a white reflective substrate (>70% reflectance) at 1550 nm TSR % Examples Over White Comparative Example 1 40.9 Comparative Example 2 32.4 Comparative Example 3 4.2 Example 3 35.7 Example 4 35.6 Example 5 35.6 Example 6 35.5 Example 7 36.0

A coating containing a conventional carbon black (Pigment Black 7) will strongly absorb at all wavelengths across the visible and NIR wavelength regions (400-2500 nm). This can be observed for Comparative Example 3 where a low TSR value is observed.

From the above, by careful consideration of the chemical composition of the pigment and the processing conditions used, solid solution pigments can be prepared. The individual inventive solid solution pigments can be seen to display highly desirable NIR non-absorbing properties, characterized by TSR values compared to existing, available, single component, black perylene pigments of Comparative Examples.

The total solar reflectance is more strongly affected by the visible and short wavelength NIR radiation than by longer wavelength NIR radiation. In other words, small differences in the absorption behavior for the inventive solid solution in the 700 to 1000 nm will have a strong influence on the TSR value.

The higher the wavelength at which the inventive solid solution pigment becomes transparent (increased reflectance over white) the lower the TSR value. For Examples 3, 4, 5, and 6, in order to improve the coloristics in the visible region, the absorption bands extend slightly into the NIR and as a result they only start to become transparent at ca. 780 nm. Examples 3, 4, 5 and 6 are therefore NIR non-absorbing across a region ca. 100 nm narrower than for Comparative Example 1, resulting in an inferior TSR value, even though the coloristics in the visible region are better. Accordingly, the inventive solid solution pigments provide good coloristics combined with good TSR performance, which makes the inventive solid solution pigments good tools for the control of NIR absorption.

It can be taken from Tables 9 and 10, for all examples based on inventive solid solutions, the NIR reflectivity and TSR values are significantly improved when compared with carbon black as illustrated by Comparative Example 3.

TABLE 11 CIELAB data of a 0.2 weight-% pigment masstone prepared according to Sample Preparation 10 over white Colour Position [SPEX 0.00 d8, over White] h C* L* a* b* Comparative Example 1 238.2 1.6 16.0 −0.9 −1.4 Comparative Example 2 41.5 0.5 16.2 0.4 0.3 Example 10 250.6 1.8 14.0 −0.6 −1.7

The inventive solid solution pigments can be seen to display highly desirable neutral to bluish black (masstone) coloristic properties, characterized by L*, a* and b* values compared to existing, available, single component, black perylene pigments of Comparative Examples 1 and 2.

TABLE 12 CIELAB data of a 1:10 weight-% pigment:titanium dioxide reduction prepared according to Sample Preparation 11 Colour Position [SPIN 0.04 d8] Strength Adjusted h C* L* a* b* Comparative Example 1 165.7 7.9 51.8 −7.6 2.0 Comparative Example 2 303.4 28.5 38.2 15.7 −23.8 Example 10 290.9 1.8 48.5 0.6 −1.7

The inventive solid solution pigment can be seen to display highly desirable neutral to bluish grey (reduction) coloristic properties, characterized by very low C*, a* and b* values compared to existing, available, single component, black perylene pigments of Comparative Examples 1 and 2.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 shows a XRD spectrum of Example 1

FIG. 2 shows a XRD spectrum of Example 2

FIG. 3 shows a XRD spectrum of Example 3

FIG. 4 shows a XRD spectrum of Example 4

FIG. 5 shows a XRD spectrum of Example 5

FIG. 6 shows a XRD spectrum of Example 6

FIG. 7 shows a XRD spectrum of Example 7

FIG. 8 shows a XRD spectrum of Example 8

FIG. 9 shows a XRD spectrum of Example 9

FIG. 10 shows a XRD spectrum of Comparative Example 1

FIG. 11 shows a XRD spectrum of Comparative Example 2

FIG. 12 shows a Pigment masstone basecoat (2.5% pigment of Examples) prepared according to Sample Preparation 6

FIG. 13 shows a 10:90 weight-% Pigment (Examples):Titanium Dioxide White Reduction prepared according to Sample Preparation 8

FIG. 14a shows all angles of a CIELAB panel of a 50:50 weight-% Pigment (Examples):Aluminium Reduction prepared according to Sample Preparation 9

FIG. 14b shows zoom in all angles of a CIELAB panel of a 50:50 weight-% Pigment:Aluminium Reduction prepared according to Sample Preparation 9

FIG. 15 shows Vis-NIR reflectance

LIST OF CITED PRIOR ART

    • WO2018/081613
    • U.S. Pat. No. 7,083,675
    • EP0636666B1
    • WO91/02034A1
    • EP2316886A1
    • EP504922A1
    • US2012018687A1
    • CN110591445A
    • Justus Liebigs Annalen der Chemie, 1984, 483
    • U.S. Pat. No. 4,450,273
    • US 2010/0184983A1
    • WO2009/074504A2

Claims

1. A solid solution comprising

(a) a compound according to formula (I)
and
(b) a compound according to formula (II), or a compound according to formula (III), or a mixture of a compound according to formula (II) and a compound according to formula (III)
wherein R1 and R2 are independently of one another —(CH2)n—X, wherein X is hydrogen, methyl, a C1-C5 alkoxyl, hydroxy, phenyl, C1-C5 alkylphenyl, C1-C5 alkoxyphenyl, hydroxyphenyl, halogenated phenyl, pyridyl, C1-C5 alkylpyridyl, C1-C5 alkoxypyridyl, halogenated pyridyl, pyridylvinyl or naphthyl; wherein n is 0, 1, 2, 3, 4 or 5; R3 and R4 are independently of one another phenylene, C1-C5 alkylphenylene, C1-C5 alkoxyphenylene, hydroxyphenylene, halogenated phenylene, pyridinediyl, C1-C5 alkylpyridinediyl, C1-C5 alkoxypyridinediyl, halogenated pyridinediyl, anthraquinonediyl or naphthalenediyl, wherein the 2 nitrogen atoms bound to R3 according to formula (II) and (III) form a 5-membered or a 6-membered heterocycle with 2 atoms of an aromatic ring of R3; wherein the 2 nitrogen atoms bound to R4 according to formula (II) and (III) form a 5-membered or a 6-membered heterocycle with 2 atoms of an aromatic ring of R4; and X1 to X8 are independently from one another hydrogen, C1-C5 alkyl, C1-C5 alkoxy, hydroxy, phenyl or halide.

2. The solid solution of claim 1, wherein

X is methoxyphenyl or phenyl and n is 1 or 2;
R3 and R4 are independently of one another phenylene, methyl-phenylene, methoxyphenylene, chloro-phenylene, dichloro-phenylene or naphthalenediyl; and
X1 to X8 are hydrogen.

3. The solid solution of claim 1, wherein

R1 and R2 are independently from one another —CH2C6H4OCH3 or —CH2CH2C6H5;
R3 and R4 are independently of one another phenylene, 4-chloro-phenylene, naphthalenediyl or 4,5-dichloro-phenylene; and
X1 to X8 are hydrogen.

4. The solid solution of claim 1, wherein

X is 4-methoxyphenyl and n is 1;
R3 and R4 are phenylene; and
X1 to X8 are hydrogen; and/or
X is 4-methoxyphenyl and n is 1;
R3 and R4 are naphthalenediyl; and
X1 to X8 are hydrogen; and/or
X is 4-methoxyphenyl and n is 1;
R3 and R4 are 4-chloro-phenylene; and
X1 to X8 are hydrogen; and/or
X is 4-methoxyphenyl and n is 1;
R3 and R4 are 4,5-dichloro-phenylene; and
X1 to X8 are hydrogen; and/or
X is phenyl and n is 2;
R3 and R4 are phenylene; and
X1 to X8 are hydrogen; and/or
X is phenyl and n is 2;
R3 and R4 are naphthalenediyl; and
X1 to X8 are hydrogen; and/or
X is phenyl and n is 2;
R3 and R4 are 4-chloro-phenylene; and
X1 to X8 are hydrogen.

5. The solid solution of claim 1, exhibiting a non-color depending black value My in the range of from 200 to 350, and a color depending black value Mc in the range of from 200 to 350, MY and MC being determined according to DIN EN 18314-3.

6. The solid solution of claim 1, wherein in the solid solution, the weight ratio of the compound of formula (I) relative to the compound according to formula (II) or to the compound according to formula (III) or to the mixture of the compound according to formula (II) and the compound according to formula (III), weight((I)):weight((II)(III)), is in the range of from 60:40 to 95:5.

7. The solid solution of claim 1, wherein from 80 to 100 weight-%, of the solid solution consist of

(a) the compound according to formula (I) and
(b) the compound according to formula (II), or the compound according to formula (III), or the mixture of the compound according to formula (II) and the compound according to formula (III).

8. A process for producing a solid solution, comprising

(i.1) providing a compound according to formula (IV)
and a suitable organic base;
(i.2) simultaneously reacting the compound of formula (IV) (i.2.1) with a compound R1—NH2, or with a compound R2—NH2, or, if R1 is different from R2, with a compound R1—NH2 and with a compound R2—NH2; and (i.2.2) with a compound H2N—R3—NH2, or with a compound H2N—R4—NH2, or, if R3 is different from R4, with a compound H2N—R3—NH2 and with a compound H2NR4—NH2, wherein the 2 nitrogen atoms bound to R3 are bound to 2 atoms of an aromatic ring of R3 and wherein the 2 nitrogen atoms bound to R4 are bound to 2 atoms of an aromatic ring of R4;
wherein R1 and R2 are independently of one another —(CH2)n—X, wherein X is hydrogen, methyl, a C1-C5 alkoxyl, hydroxy, phenyl, C1-C5 alkylphenyl, C1-C5 alkoxyphenyl, hydroxyphenyl, halogenated phenyl, pyridyl, C1-C5 alkylpyridyl, C1-C5 alkoxypyridyl, halogenated pyridyl, pyridylvinyl or naphthyl; wherein n is 0, 1, 2, 3, 4 or 5; R3 and R4 are independently of one another phenylene, C1-C5 alkylphenylene, C1-C5 alkoxyphenylene, hydroxyphenylene, halogenated phenylene, pyridinediyl, C1-C5 alkylpyridinediyl, C1-C5 alkoxypyridinediyl, halogenated pyridinediyl, anthraquinonediyl or naphthalenediyl; and X1 to X8 are independently from one another hydrogen, C1-C5 alkyl, C1-C5 alkoxy, hydroxy, phenyl or halide.

9. The process of claim 8, wherein the compound of formula (IV) is provided as a solid.

10. The process of claim 8, further comprising, after (i.1) and before (i.2), preparing a suspension comprising

the compound according to formula (IV); and
the compound R1—NH2, or the compound R2—NH2, or, if R1 is different from R2, the compound R1—NH2 and the compound R2—NH2; and
the compound H2N—R3—NH2, or the compound H2N—R4—NH2, or, if R3 is different from R4, the compound H2N—R3—NH2 and the compound H2N—R4—NH2; and
water.

11. The process of claim 8, further comprising, after (i.1) and before (i.2), preparing a solution comprising

the compound according to formula (IV); and
the compound R1—NH2, or the compound R2—NH2, or, if R1 is different from R2, the compound R1—NH2 and the compound R2—NH2; and
the compound H2N—R3—NH2, or the compound H2N—R4—NH2, or, if R3 is different from R4, the compound H2N—R3—NH2 and the compound H2N—R4—NH2, and
a suitable inorganic base.

12. The process of claim 8, wherein the suitable organic base comprises a secondary or tertiary amine.

13. The process of claim 8, wherein the reaction according to (i.2) is carried out in the presence of 95 to 5 weight-% of the compound R1—NH2, or of the compound R2—NH2, or, if R1 is different from R2, of the compound R1—NH2 and of the compound R2—NH2; and

in the presence of 5 to 95 weight-%, of the compound H2N—R3—NH2, or the compound H2N—R4—NH2, or, if R3 is different from R4, the compound H2N—R3—NH2 and the compound H2N—R4—NH2.

14. The process of claim 8, wherein the reaction according to (i.2) is carried out at a temperature of the reaction mixture, in the range of from 80 to 210° C., at a pressure in the range of from 1 to 20 bar (100 to 2000 kPa).

15. The process of claim 8, further comprising

(i) providing a mixture comprising the solid solution obtained from (i.2);
(ii) subjecting the mixture provided according to (i) to mechanical treatment;
(iii) adding water to the mixture obtained from (ii);
(iv) subjecting the mixture obtained from (iii) to solid-liquid separation;
(v) washing the solids obtained from (iv) with at least one suitable washing agent; and
(vi) drying the solids obtained from (v), obtaining the solid solution.

16. The process of claim 8, wherein the mechanical treatment according to (ii) comprises one or more kneading and milling, wherein kneading comprises coextrusion, salt kneading, single-shaft kneading and double-shaft kneading and wherein milling comprises wet milling, ball milling, bead milling, vibration milling, planetary milling and attritor milling.

17. The process of claim 8, wherein the mechanical treatment according to (ii) comprises kneading, wherein said kneading is carried out at a temperature of the mixture in the range of from 40 to 120° C.

18. The process of claim 8, wherein the mechanical treatment according to (ii) further comprises, either directly before and/or during kneading, adding at least one or more of a synergist comprising sulfonic and carboxylic acid derivatives of perylene, indanthrone, phthalocyanine and diketopyrrolopyrrole.

19. A solid solution obtained by a process according to claim 8.

20. An article comprising a solid solution according to claim 1, wherein the article is selected from the group consisting of a coating composition, a light detection and ranging (LiDAR) device, a near-infrared (NIR) non-absorbing component, a photovoltaic component, a heat management component, a thermal insulation component, a coloring paint, a printing ink, a recyclable plastic article, a biodegradable mulch, a toner, a charge-generating material, a color filter, a LC display and a security print component.

21. A method to increase the signal to noise ratio in near-infrared (NIR) radiation detection in a coating or object, comprising replacing the near-infrared (NIR) absorbing black pigments in the coating or object with a solid solution of claim 1.

22. A multilayer coating comprising:

a primer coating comprising a solid solution according to claim 1 and a white pigment or a reflective pigment having a reflectance of >50% in the range of 700 to 2500 nm, in a weight ratio of from 1:99 to 99:1;
a basecoat comprising a black color, metallic or interference pigment; and
optionally a clear topcoat.

23. A solid solution according to claim 1, comprised in one or more of a thermoplastic, elastomeric, crosslinked or inherently crosslinked polymer in an amount from 0.01 weight-% to 70 weight-% based on the total weight of the polymer.

Patent History
Publication number: 20240026171
Type: Application
Filed: Dec 20, 2021
Publication Date: Jan 25, 2024
Applicant: SUN CHEMICAL B.V. (Weesp)
Inventors: Nikolay VINOKUROV (Ludwigshafen am Rhein), Paul Pascal ROQUETTE (Ludwigshafen am Rhein), Paul BROWN (Basel), Till VOGEL (Ludwigshafen am Rhein), Andres Carlos GARCIA ESPINO (Ludwigshafen am Rhein)
Application Number: 18/256,559
Classifications
International Classification: C09D 7/41 (20060101); C09B 67/22 (20060101); C09B 3/18 (20060101); C09D 5/33 (20060101); C09D 5/00 (20060101); C09D 5/36 (20060101);